Dyeing compositions for keratinous fibres containing paraphenylenediamine derivatives with pyrrolidinyl group

ABSTRACT

The invention concerns novel dyeing compositions for keratinous fibers comprising at least a paraphenylenediamine derivative with pyrrolidinyl group as oxidation base, a dyeing method and a dyeing kit using said composition.

[0001] The invention relates to novel compositions for the oxidationdyeing of keratin fibers, comprising at least one para-phenylenediaminederivative containing a pyrrolidinyl group as oxidation base, to adyeing process and to a dyeing kit using this composition.

[0002] It is known practice to dye keratin fibers, and in particularhuman hair, with dye compositions containing oxidation dye precursors,in particular ortho- or para-phenylenediamines, ortho- orpara-aminophenols, and heterocyclic bases such as diaminopyrazolederivatives, which are generally known as oxidation bases. Theseoxidation dye precursors (oxidation bases) are colorless or weaklycolored compounds which, when combined with oxidizing products, can giverise to colored compounds and dyes by a process of oxidativecondensation.

[0003] It is also known that the shades obtained with these oxidationbases can be varied by combining them with couplers or colorationmodifiers, the latter being chosen in particular from aromaticmeta-diamines, meta-aminophenols, meta-diphenols and certainheterocyclic compounds.

[0004] The variety of molecules used as oxidation bases and couplersallows a wide range of colors to be obtained.

[0005] The so-called “permanent” coloration obtained by means of theseoxidation dyes should moreover satisfy a certain number of requirements.Thus, it should have no toxicological drawbacks, it should allow shadesto be obtained in the desired intensity and it should have good stayingpower with respect to external agents (light, bad weather, washing,permanent-waving, perspiration or rubbing).

[0006] The dyes should also allow gray hair to be covered and, finally,they should be as unselective as possible, i.e. they should allow onlythe smallest possible differences in coloration to be obtained along thesame keratin fiber, which may indeed be differently sensitized (i.e.damaged) between its tip and its root.

[0007] In the field of hair dyeing, para-phenylenediamine andpara-toluylenediamine are oxidation bases that are widely used. Withoxidation couplers, they make it possible to obtain a variety of shades.

[0008] However, there is a need to discover novel oxidation bases, alsoknown as developers, which have a better toxicological profile thanpara-phenylenediamine or para-toluylenediamine, while at the same timemaking it possible to give the hair excellent properties of colorintensity, of variety of shades, of color uniformity and of stayingpower with respect to external agents.

[0009] It has already been proposed, especially in patent application GB2 239 265, to use 2-(β-hydroxyethyl)-para-phenylenediamine orN,N-bis(β-hydroxyethyl)-para-phenylenediamine as potential replacementsfor para-phenylenediamine and para-toluylenediamine. This is likewisethe case for 2-(hydroxyalkoxy)-para-phenylenediamines (see especiallyU.S. Pat. No. 5,538,516).

[0010] However, N,N-bis-(β-hydroxyethyl)-para-phenylenediamine and2-(β-hydroxyethyl)-para-phenylenediamine nevertheless have the drawbackof giving a more limited variety of shades and of giving less colorintensity and less uniformity to the hair than para-phenylenediamine orpara-toluylenediamine. It is likewise the case for2-(hydroxyalkoxy)-para-phenylenediamines, which give the hair a colorwhich evolves and changes over time.

[0011] Moreover, it is known from the literature, see R. L. Bent et al.,J.A.C.S. 73, 3100, 1951, that para-phenylenediamine derivatives in whichone of the nitrogen atoms is included in a non-aromatic 6- or 7-memberedcarbon-based or heterocyclic ring are less oxidizable thanpara-phenylenediamine derivatives in which one of the nitrogen atoms issubstituted with two disymmetric substituents, which are themselves lessoxidizable than para-phenylenediamine derivatives in which one of thenitrogen atoms is substituted with two symmetrical substituents.

[0012] It is also mentioned in the same article that thepara-phenylenediamine derivative in which one of the nitrogen atoms isincluded in a non-aromatic 5-membered carbon-based ring is moreoxidizable than each of the derivatives mentioned above. This particularclass of N-pyrrolidine derivatives of para-phenylenediamine thus makesit possible to obtain kinetically accelerated condensation reactionswith couplers in basic and oxidative medium when compared with thepara-phenylenediamine derivatives mentioned above.

[0013] However, oxidation bases which are too oxidizable and which reactwith couplers at accelerated reaction rates generally lead to theformation of dyes on the exterior of the keratin fiber. Intensities,staying power and uniformity of the colorations thus obtained on thehair are generally insufficient. However, U.S. Pat. No. 5,851,237proposes the use of 1-(4-aminophenyl)pyrrolidine derivatives optionallysubstituted on the benzene nucleus, in order to replacepara-phenylenediamine. In this respect, the same patent verypreferentially proposes to use 1-(4-amino-phenyl)pyrrolidine as areplacement for para-phenylenediamine.

[0014] Now, it is known in the literature that1-(4-aminophenyl)pyrrolidine has highly allergenic activity (R. L. Bentet al., J.A.C.S. 73, 3100, 1951).

[0015] U.S. Pat. No. 5,993,491 also proposes the use ofN-(4-aminophenyl)-2-(hydroxymethyl)pyrrolidines optionally substitutedon the benzene nucleus, in order to replace para-phenylenediamine. Asvery preferential compounds claimed, said patent proposesN-(4-aminophenyl)-2-(hydroxymethyl)pyrrolidine optionally substitutedwith a methyl radical in position 3.

[0016] However, it has been clearly established that these compounds donot make it possible to give the hair a coloration of equivalent qualityto that obtained with para-phenylenediamine, due to a lack of intensityand uniformity of the color obtained.

[0017] Patent application JP 11 158 048 also proposes hair-coloringcompositions which offer good properties of spreading, ease ofapplication and resistance to shampoo. These dye compositions contain atleast one compound chosen from para-phenylenediamine derivativesoptionally substituted with 1 to 4 substituents on the benzene nucleusand one of the nitrogen atoms of which is included in a 5- to 7-memberedcarbon-based ring, or from para-phenylenediamine derivatives optionallysubstituted with 1 to 4 substituents on the benzene nucleus and one ofthe nitrogen atoms of which is substituted with a radical Z₁ and aradical Z₂, Z₁ being an alkyl or aryl group or a heterocycle, and Z₂being a radical —(CH₂—CH₂—O)—Z₃ in which Z₃ represents a hydrogen atom,an alkyl or aryl group or a heterocycle.

[0018] In terms of coloring power, ease of application, uniformity ofthe coloration obtained and staying power especially with respect to theaction of shampoos. It is seen in this Japanese patent application thatthe preferred derivatives, namelyN-(3-isopropyloxy-4-aminophenyl)-2,5-diethylpyrrolidine,N-(3-methyl-4-aminophenyl)-3-(2-hydroxyethyl-oxy)pyrrolidine andN-(3-methyl-4-aminophenyl)-2-methyl-4-hydroxypyrrolidine behave likeoxidation bases equivalent to 4-aminoaniline derivatives in which thenitrogen atom is included in a functionalized 6-membered piperidinering.

[0019] However, it is known that when one of the nitrogen atoms of thepara-phenylenediamine derivatives is included in a 6-membered ring, theactivation energy to lead to the corresponding quinone-imine oxidizedform is among the highest in the N,N-disubstituted para-phenylenediamineseries. The consequence of these data is that the condensation reactionswith couplers are less efficient and give the hair insufficient coloringproperties in terms of intensity and uniformity of the color obtained,when compared with those obtained with para-phenylenediamine orpara-toluylenediamine.

[0020] The result of this is that the solutions proposed in patentapplication JP 11 158 048, by means of para-phenylenediamine derivativeshaving a nitrogen atom included in a functionalized pyrrolidine ring, donot make it possible to give the hair dyeing results that are equivalentto those obtained with para-phenylenediamine or para-toluylenediamine.

[0021] It is thus clear that there is a real need to discover noveloxidation bases that have both a good toxicological profile andproperties such that the compositions containing them make it possibleto give the hair colorations with excellent properties of colorintensity, of variety of shades, of color uniformity (that is to say alow selectivity) and of staying power with respect to the variousexternal attacking factors to which the hair may be subjected.

[0022] The applicant has now discovered, entirely surprisingly andunexpectedly, that certain para-phenylenediamine derivatives containinga pyrrolidinyl group of formula (I) defined below, are not only suitedfor use as oxidation bases for the oxidation dyeing of keratin fibers,but also lead to particularly powerful and relatively unselectivecolorations. They moreover make it possible to obtain dye compositionswhich give colorations that are resistant to the various attackingfactors to which the hair may be subjected.

[0023] These discoveries form the basis of the present invention.

[0024] A first subject of the invention is thus a composition for theoxidation dyeing of keratin fibers, and in particular of human keratinfibers such as the hair, characterized in that it comprises, in a mediumwhich is suitable for dyeing, at least one oxidation base chosen frompara-phenylenediamine derivatives containing a pyrrolidinyl group offormula (I) below, and the addition salts thereof with an acid:

[0025] in which:

[0026] R₁ represents a hydrogen atom; a halogen atom chosen from achlorine atom and a bromine atom; a linear or branched C₁-C₇ alkylradical, the branch(es) possibly forming one or more 3- to 5-memberedcarbon-based rings, which may contain one or more double bonds and/orone or more triple bonds, said double bonds optionally being able tolead to aromatic groups, one or more carbon atoms of which may bereplaced with an oxygen, nitrogen or sulfur atom or with an SO₂ group,and the carbon atoms of which may be, independently of each other,substituted with one or more halogen atoms; said radical R₁ containingno peroxide bond or diazo, nitro or nitroso radicals;

[0027] R₂ represents a hydroxyl radical; an amino radical; a group —OR₃in which R₃ represents a linear or branched C₁-C₄ alkyl radicalsubstituted with one or more radicals chosen from the group consistingof a halogen atom, C₁-C₂ alkoxy, amino or C₁-C₂ aminoalkyl or a C₃-C₄alkyl radical substituted with one or more hydroxyl radicals; a group—NR₄R₅ in which R₄ and R₅ represent, independently of each other, ahydrogen atom, a linear or branched C₁-C₄ alkyl radical substituted withone or more radicals chosen from the group consisting of a halogen atomand a hydroxyl, C₁-C₂ alkoxy, amino or C₁-C₂ aminoalkyl radical.

[0028] As mentioned above, the colorations obtained with the oxidationdye composition in accordance with the invention are powerful andrelatively unselective and also have excellent properties of resistancewith respect to the action of the various external agents (light, badweather, washing, permanent-waving, perspiration and rubbing). Theoxidation dye compositions in accordance with the invention furthermoremake it possible to achieve shades in a very broad range of colors.

[0029] According to the invention, when it is indicated that one or moreof the carbon atoms of the radical R₁ can be replaced with an oxygen,nitrogen or sulfur atom or with an SO₂ group, and/or when said radicalR₁ can contain one or more double bonds and/or one or more triple bonds,this means that, for example, the following conversions can be carriedout;

can become

can become

can become

can become

[0030] In particular, R₁ may be chosen from a hydrogen atom, a linear orbranched, saturated or unsaturated hydrocarbon-based chain, alkoxy,alkoxyalkyl, mono- or polyhydroxyalkyl, aminoalkyl, carboxyalkyl,hydroxyaminoalkyl and hydroxyalkoxy groups. Among these substituents, R₁may especially represent a hydrogen atom or a methyl, ethyl, isopropyl,vinyl, allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl,1-aminomethyl, 2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl,1,2-dihydroxyethyl, 1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or3-hydroxyethyloxy radical. Among these substituents, R₁ preferablyrepresents a hydrogen atom or a methyl, hydroxymethyl, 2-hydroxyethyl,1,2-dihydroxyethyl, methoxy or 2-hydroxyethoxy radical.

[0031] Among these substituents, R₁ even more preferentially representsa hydrogen atom or a methyl radical.

[0032] Among the substituents R₂ that are useful for the invention, R₂represents a hydroxyl radical; an amino radical; a group —OR₃ in whichR₃ represents a linear or branched C₁-C₄ alkyl radical substituted withone or more radicals chosen from the group consisting of a halogen atom,C₁-C₂ alkoxy, amino and C₁-C₂ aminoalkyl; a group —NR₄R₅ in which R₄ andR₅ represent, independently of each other, a hydrogen atom, a linear orbranched C₁-C₄ alkyl radical substituted with one or more radicalschosen from the group consisting of a halogen atom and a hydroxyl, C₁-C₂alkoxy, amino or C₁-C₂ aminoalkyl radical. Preferably, R₂ represents ahydroxyl, acetoxy, amino, methylamino, dimethylamino or2-hydroxyethylamino radical. Among these substituents, R₂ even morepreferentially represents a hydroxyl or amino radical.

[0033] Among the para-phenylenediamine derivatives containing apyrrolidinyl group of formula (I) above, mention may be made especiallyof N-(4-aminophenyl)-3-hydroxypyrrolidine,N-(4-amino-2-methylphenyl)-3-hydroxypyrrolidine,N-(4-amino-2-ethylphenyl)-3-hydroxypyrrolidine,N-(4-amino-2-methoxyphenyl)-3-hydroxypyrrolidine,N-(4-amino-2-(2-hydroxy-ethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-2-(1-hydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-2-(1,2-dihydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-methylphenyl)-3-hydroxypyrrolidine,N-(4-amino-3-ethylphenyl)-3-hydroxypyrrolidine,N-(4-amino-3-methoxyphenyl)-3-hydroxypyrrolidine,N-(4-amino-3-(2-hydroxy-ethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-(1-hydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-(1,2-dihydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-aminophenyl)-3-aminopyrrolidine,N-(4-amino-2-methylphenyl)-3-aminopyrrolidine,N-(4-amino-2-ethylphenyl)-3-aminopyrrolidine,N-(4-amino-2-methoxyphenyl)-3-aminopyrrolidine,N-(4-amino-2-(2-hydroxyethyl)-phenyl)-3-aminopyrrolidine,N-(4-amino-2-(1-hydroxy-ethyl)phenyl)-3-aminopyrrolidine,N-(4-amino-2-(1,2-dihydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-methylphenyl)-3-aminopyrrolidine,N-(4-amino-3-ethylphenyl)-3-aminopyrrolidine,N-(4-amino-3-methoxyphenyl)-3-aminopyrrolidine,N-(4-amino-3-(2-hydroxyethyl)phenyl)-3-amino-pyrrolidine,N-(4-amino-3-(1-hydroxyethyl)phenyl)-3-aminopyrrolidine andN-(4-amino-3-(1,2-dihydroxyethyl)phenyl)-3-aminopyrrolidine, and theaddition salts thereof with an acid.

[0034] The para-phenylenediamine derivatives containing a pyrrolidinylgroup of formula (I), and processes for synthesizing them, are known;see in particular patent application DE 4 241 532 (AGFA).

[0035] The para-phenylenediamine derivative(s) containing a pyrrolidinylgroup of formula (I) in accordance with the invention and/or theaddition salt(s) thereof with an acid preferably represent(s) from0.0005% to 12% by weight approximately relative to the total weight ofthe dye composition, and even more preferentially from 0.005% to 6% byweight approximately relative to this weight.

[0036] The medium which is suitable for dyeing (or support) generallyconsists of water or of a mixture of water and at least one organicsolvent to dissolve the compounds which would not be sufficientlywater-soluble. Organic solvents which may be mentioned, for example,include C₁-C₄ lower alkanols, such as ethanol and isopropanol; glycerol;glycols and glycol ethers, for instance 2-butoxyethanol, propyleneglycol, propylene glycol monomethyl ether and diethylene glycolmonoethyl ether and monomethyl ether, and also aromatic alcohols, forinstance benzyl alcohol or phenoxyethanol, similar products and mixturesthereof.

[0037] The solvents may be present in proportions preferably of between1% and 40% by weight approximately relative to the total weight of thedye composition, and even more preferentially between 5% and 30% byweight approximately.

[0038] The pH of the dye composition in accordance with the invention isgenerally between 3 and 12 approximately and preferably between 5 and 11approximately. It may be adjusted to the desired value by means ofacidifying or basifying agents usually used in the dyeing of keratinfibers, or alternatively using conventional buffer systems.

[0039] Among the acidifying agents which may be mentioned, for example,are mineral or organic acids, for instance hydrochloric acid,orthophosphoric acid, sulfuric acid, carboxylic acids, for instanceacetic acid, tartaric acid, citric acid and lactic acid, and sulfonicacids.

[0040] According to one particular embodiment, the basifying agents arechosen from alkanolamines, diaminoalkanes and aqueous ammonia.

[0041] For the purposes of the present invention, the term“alkanolamine” means any saturated or unsaturated, linear or branchedhydrocarbon-based compound containing from 2 to 100 carbon atoms andcomprising (i) at least one amine function optionally substituted withone or two substituents which are preferably C₁-C₄ alkyl or substitutedC₁-C₄ alkyl, such as, for example, mono- or polyhydroxyalkyl, and (ii)at least one hydroxyl function not borne by the amine function.Preferably, the hydrocarbon-based chain is saturated.

[0042] Among the alkanolamines which may be used according to theinvention, mention may be made of monoethanolamine, diethanolamine,triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,2-amino-1-butanol, tris(hydroxy-methyl)aminomethane,2-aminoethylethanolamine, 1-diethylamino-2,3-propanediol,2-dimethylamino-2-methyl-1-propanol, dimethylethanolamine,diethylethanolamine, ethylmonoethanolamine and methylethanolamine.Preferably, monoethanolamine is used.

[0043] The diaminoalkanes used according to the invention are preferablythe diaminoalkanes of formula (II) below:

[0044] in which W is an alkylene residue optionally substituted with ahydroxyl group or a C₁-C₄ alkyl radical; R₅, R₆, R₇ and R₈, which may beidentical or different, represent a hydrogen atom, a C₁-C₄ alkyl radicalor a C₁-C₄ hydroxyalkyl radical. Preferably, W is a propylene residue.Even more preferentially, the diaminoalkane is diaminopropane.

[0045] Among all the alkaline agents which may be used according to theinvention, aqueous ammonia is preferably used.

[0046] The alkaline agent(s) is (are) present in the ready-to-useoxidation dye composition or the composition intended for oxidationdyeing according to the invention in concentrations ranging from about0.1% to about 20% by weight, and preferably from about 0.5% to about 10%by weight of active material relative to the total weight of thecomposition intended for oxidation dyeing or the ready-to-use oxidationdye composition.

[0047] According to one preferred embodiment, the oxidation dyecomposition in accordance with the invention also contains one or morecouplers so as to modify the shades obtained by using the compounds offormula (I), or to enrich the shades with glints.

[0048] The couplers which may be used in the oxidation dye compositionsin accordance with the invention may be chosen from couplersconventionally used in oxidation dyeing, and among which mention may bemade especially of meta-phenylenediamines, meta-aminophenols,meta-diphenols, naphthols and heterocyclic couplers such aspyrazolo[1,5-b]-1,2,4-triazoles, pyrazolo[3,2-c]-1,2,4-triazoles,pyrazol-5-ones, pyridines, indoles, indolines, indazoles,benzimidazoles, benzothiazoles, benzoxazoles, 1,3-benzodioxoles andquinolines.

[0049] According to one particular embodiment, the coupler(s) is (are)chosen from heterocyclic couplers, substituted meta-diphenols,substituted meta-phenylenediamines, naphthols and acylated naphthols,and the meta-aminophenols of formula (III) below, and the addition saltsthereof with an acid:

[0050] in which:

[0051] R₅ represents a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄monohydroxyalkyl or C₂-C₄ polyhydroxyalkyl radical,

[0052] R₆ represents a hydrogen atom, a C₁-C₄ alkyl or C₁-C₄ alkoxyradical or a halogen atom chosen from chlorine, bromine and fluorine,

[0053] R₇ represents a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄ alkoxy,C₁-C₄ monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, C₁-C₄ monohydroxyalkoxyor C₂-C₄ polyhydroxyalkoxy radical.

[0054] Among the substituted meta-diphenols which may be used ascouplers in the dye composition in accordance with the invention, thecompounds which will preferably be used are those of formula (VI) below,and the addition salts thereof with an acid.

[0055] in which:

[0056] R₈ and R₉, which may be identical or different, represent ahydrogen atom, a C₁-C₄ alkyl radical or a halogen atom chosen fromchlorine, bromine and fluorine, it being understood that at least one ofthe radicals R₈ and R₉ is other than a hydrogen atom.

[0057] Among the substituted meta-diphenols of formula (VI) above whichmay be mentioned more particularly are 2-methyl-1,3-dihydroxybenzene,4-chloro-1,3-dihydroxybenzene and 2-chloro-1,3-dihydroxybenzene, and theaddition salts thereof with an acid.

[0058] Among the substituted meta-phenylenediamines which may be used ascouplers in the dye composition in accordance with the invention, thecompounds which will preferably be used are those of formula (V) below,and the addition salts thereof with an acid:

[0059] in which:

[0060] R₁₀ represents a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄monohydroxyalkyl or C₂-C₄ polyhydroxyalkyl radical;

[0061] R₁₁ and R₁₂, which may be identical or different, represent ahydrogen atom or a C₁-C₄ alkyl, C₁-C₄ monohydroxyalkoxy or C₂-C₄polyhydroxyalkoxy radical;

[0062] R₁₃ represents a hydrogen atom, a C₁-C₄ alkoxy, C₁-C₄aminoalkoxy, C₁-C₄ monohydroxyalkoxy or C₂-C₄ polyhydroxalkoxy radicalor a 2,4-diaminophenoxyalkoxy radical; it being understood that at leastone of the radicals R₁₀ to R₁₃ is other than a hydrogen atom.

[0063] Among the substituted meta-phenylenediamines of formula (V) abovewhich may be mentioned more particularly are3,5-diamino-1-ethyl-2-methoxybenzene, 3,5-diamino2-methoxy-1-methylbenzene, 2,4-diamino-1-ethoxybenzene,1,3-bis(2,4-diaminophenoxy)propane, bis(2,4-diaminophenoxy)methane,1-(β-aminoethyloxy)-2,4-diaminobenzene,2-amino-1-(β-hydroxyethyloxy)-4-methylaminobenzene,2,4-diamino-1-ethoxy-5-methyl-benzene,2,4-diamino-5-(β-hydroxyethyloxy)-1-methylbenzene,2,4-diamino-1-(β,γ-dihydroxypropyloxy)benzene,2,4-diamino-1-(β-hydroxyethyloxy)benzene and2-amino-4-N-(β-hydroxyethyl)amino-1-methoxybenzene, and the additionsalts thereof with an acid.

[0064] Among the heterocyclic couplers which may be used in the dyecomposition in accordance with the invention, mention may be madeespecially of indole derivatives, indoline derivatives, benzimidazolederivatives, benzomorpholine derivatives, sesamol derivatives,pyrazoloazole derivatives, pyrroloazole derivatives, imidazoloazolederivatives, pyrazolopyrimidine derivatives, pyrazolin-3,5-dionederivatives, pyrrolo[3,2-d]oxazole derivatives, pyrazolo[3,4-d]thiazolederivatives, thiazoloazole S-oxide derivatives and thiazoloazoleS,S-dioxide derivatives, and the addition salts thereof with an acid.

[0065] Among the indole derivatives which may be used as heterocycliccouplers in the dye composition in accordance with the invention,mention may be made particularly of the compounds of formula (VI) below,and the addition salts thereof with an acid:

[0066] in which:

[0067] R₁₄ represents a hydrogen atom, a C₁-C₄ alkyl, C₁-C₄monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl or C₁-C₄ aminoalkyl radical inwhich the amine is mono- or disubstituted with a C₁-C₄ alkyl group;

[0068] R₁₅ represents a hydrogen atom or a C₁-C₄ alkyl radical;

[0069] R₁₆ represents a hydrogen atom or a C₁-C₄ alkyl or hydroxylradical;

[0070] X represents a hydroxyl radical or a radical NHR₁₇ in which R₁₇represents a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkylradical.

[0071] Among the indole derivatives of formula (V) above which may bementioned more particularly are 4-hydroxyindole, 6-hydroxyindole,7-aminoindole, 6-aminoindole, 7-hydroxyindole,7-ethyl-6-(β-hydroxyethyl)aminoindole, 4-aminoindole,6-hydroxy-1-methylindole, 5,6-dihydroxyindole,4-hydroxy-1-N-methylindole, 4-hydroxy-2-methylindole,4-hydroxy-5-methylindole, 4-hydroxy-1-N-(β-hydroxyethyl)indole,4-hydroxy-1-N-(β-hydroxypropyl)indole,1-N-(β,γ-dihydroxypropyl)-4-hydroxyindole,4-hydroxy-1-N-(β-hydroxyethyl)-5-methylindole and1-N-(γ-dimethylaminopropyl)-4-hydroxyindole, and the addition saltsthereof with an acid.

[0072] Among the indoline derivatives which may be used as heterocycliccouplers in the dye composition in accordance with the invention,mention may be made particularly of 4-hydroxyindoline,6-hydroxyindoline, 6-aminoindoline and 5,6-dihydroxyindoline, and theaddition salts thereof with an acid.

[0073] Among the benzimidazole derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compounds offormula (VII) below, and the addition salts thereof with an acid:

[0074] in which:

[0075] R₁₈ represents a hydrogen atom or a C₁-C₄ alkyl radical,

[0076] R₁₉ represents a hydrogen atom or a C₁-C₄ alkyl or phenylradical,

[0077] R₂₀ represents a hydroxyl, amino or methoxy radical,

[0078] R₂₁ represents a hydrogen atom or a hydroxyl, methoxy or a C₁-C₄alkyl radical, with the proviso that:

[0079] when R₂₀ denotes an amino radical, then it occupies position 4,

[0080] when R₂₀ occupies position 4, then R₂₁ occupies position 7,

[0081] when R₂₀ occupies position 5, then R₂₁ occupies position 6.

[0082] Among the benzimidazole derivatives of formula (VII) above,mention may be made more particularly of 4-hydroxybenzimidazole,4-aminobenzimidazole, 4-hydroxy-7-methylbenzimidazole,4-hydroxy-2-methylbenzimidazole, 1-butyl-4-hydroxybenzimidazole,4-amino-2-methylbenzimidazole, 5,6-dihydroxybenzimidazole,5-hydroxy-6-methoxybenzimidazole, 4,7-dihydroxybenzimidazole,4,7-dihydroxy-1-methylbenzimidazole, 4,7-dimethoxybenzimidazole,5,6-dihydroxy-1-methylbenzimidazole, 5,6-dihydroxy-2-methylbenzimidazoleand 5,6-dimethoxybenzimidazole, and the addition salts thereof with anacid,

[0083] Among the benzomorpholine derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compounds offormula (VIII) below, and the addition salts thereof with an acid:

[0084] in which:

[0085] R₂₂ and R₂₃, which may be identical or different, represent ahydrogen atom or a C₁-C₄ alkyl radical,

[0086] Z represents a hydroxyl or amino radical.

[0087] Among the benzomorpholine derivatives of formula (VIII) abovewhich may be mentioned more particularly are6-hydroxy-1,4-benzomorpholine, N-methyl-6-hydroxy-1,4-benzomorpholineand 6-amino-1,4-benzomorpholine, and the addition salts thereof with anacid.

[0088] Among the sesamol derivatives which may be used as heterocycliccouplers in the dye composition in accordance with the invention,mention may be made particularly of the compounds of formula (IX) below,and the addition salts thereof with an acid:

[0089] in which:

[0090] R₂₄ denotes a hydroxyl, amino, C₁-C₄ alkylamino, C₁-C₄monohydroxyalkylamino or C₂-C₄ polyhydroxyalkylamino radical,

[0091] R₂₅ denotes a hydrogen or halogen atom or a C₁-C₄ alkoxy radical.

[0092] Among the sesamol derivatives of formula (IX) above which may bementioned more particularly are 2-bromo-4,5-methylenedioxyphenol,2-methoxy-4,5-methylenedioxyaniline and2-(β-hydroxyethyl)amino-4,5-methylenedioxybenzene, and the additionsalts thereof with an acid.

[0093] Among the pyrazoloazole derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compoundsdescribed in the following patents and patent applications: FR-A-2 075583, EP-A-0 119 860, EP-A-0 285 274, EP-A-0 244 160, EP-A-0 578 248, GB1 458 377, U.S. Pat. Nos. 3,227,554, 3,419,391, 3,061,432, 4,500,630,3,725,067, 3,926,631, 5,457,210, JP 84/99437, JP 83/42045, JP 84/162548,JP 84/171956, JP 85/33552, JP 85/43659, JP 85/172982, JP 85/190779 aswell as in the following publications: Chem. Ber. 32, 797 (1899), Chem.Ber. 89, 2550, (1956), J. Chem. Soc. Perkin trans 1, 2047, (1977), J.Prakt. Chem., 320, 533, (1978); the teachings of which form an integralpart of the present patent application.

[0094] Pyrazoloazole derivatives which may be mentioned mostparticularly are:

[0095] 2-methylpyrazolo[1,5-b]-1,2,4-triazole,

[0096] 2-ethylpyrazolo[1,5-b]-1,2,4-triazole,

[0097] 2-isopropylpyrazolo[1,5-b]-1,2,4-triazole,

[0098] 2-phenylpyrazolo[1,5-b]-1,2,4-triazole,

[0099] 2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,

[0100] 7-chloro-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,

[0101] 3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole,

[0102] 6-phenyl-3-methylthiopyrazolo[3,2-c]-1,2,4-triazole,

[0103] 6-aminopyrazolo[1,5-a]benzimidazole,

[0104] and the addition salts thereof with an acid.

[0105] Among the pyrroloazole derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compoundsdescribed in the following patent applications and patents: U.S. Pat.No. 5,256,526, EP-A-0 557 851, EP-A-0 578 248, EP-A-0 518 238, EP-A-0456 226, EP-A-0 488 909, EP-A-0 488 248, and in the followingpublications:

[0106] D. R. Liljegren Ber. 1964, 3436;

[0107] E. J. Browne, J.C.S., 1962, 5149;

[0108] P. Magnus, J.A.C.S., 1990, 112, 2465;

[0109] P. Magnus, J.A.C.S., 1987, 109, 2711;

[0110] Angew. Chem. 1960, 72, 956; and

[0111] Rec. Trav. Chim. 1961, 80, 1075; the teachings of which form anintegral part of the present patent application.

[0112] Pyrroloazole derivatives which may be mentioned most particularlyare:

[0113] 5-cyano-4-ethoxycarbonyl-8-methylpyrrolo[1,2-b]-1,2,4-triazole,

[0114] 5-cyano-8-methyl-4-phenylpyrrolo[1,2-b]-1,2,4-triazole,

[0115] 7-amido-6-ethoxycarbonylpyrrolo[1,2-a]benzimidazole,

[0116] and the addition salts thereof with an acid.

[0117] Among the imidazoloazole derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compoundsdescribed in the following patent applications and patents: U.S. Pat.No. 5,441,863; JP 62-279 337; JP 06-236 011 and JP 07-092 632, theteachings of which form an integral part of the present patentapplication.

[0118] Imidazoloazole derivatives which may be mentioned mostparticularly are:

[0119] 7,8-dicyanoimidazolo[3,2-a]imidazole,

[0120] 7,8-dicyano-4-methylimidazolo[3,2-a]imidazole,

[0121] and the addition salts thereof with an acid.

[0122] Among the pyrazolopyrimidine derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compoundsdescribed in the following patent application: EP-A-0 304 001, theteaching of which forms an integral part of the present patentapplication.

[0123] Pyrazolopyrimidine derivatives which may be mentioned mostparticularly are:

[0124] pyrazolo[1,5-a]pyrimidin-7-one,

[0125] 2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-one,

[0126] 2-methyl-6-ethoxycarbonylpyrazolo[1,5-a]pyrimidin-7-one,

[0127] 2-methyl-5-methoxymethylpyrazolo[1,5-a]pyrimidin-7-one,

[0128] 2-tert-butyl-5-trifluoromethylpyrazolo[1,5-a]pyrimidin-7-one,

[0129] 2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one,

[0130] and the addition salts thereof with an acid.

[0131] Among the pyrazoline-3,5-dione derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compoundsdescribed in the following patent applications and patents: JP07-036159, JP 07-084348 and U.S. Pat. No. 4,128,425, and in thefollowing publications:

[0132] L. WYZGOWSKA, Acta. Pol. Pharm. 1982, 39 (1-3), 83.

[0133] E. HANNIG, Pharmazie, 1980, 35 (4), 231

[0134] M. H. ELNAGDI, Bull. Chem. Soc. Jap., 46 (6), 1830, 1973

[0135] G. CARDILLO, Gazz. Chim. Ital. 1966, 96, (8-9), 973, theteachings of which form an integral part of the present patentapplication.

[0136] Pyrazoline-3,5-dione derivatives which may be mentioned mostparticularly are:

[0137] 1,2-diphenylpyrazoline-3,5-dione,

[0138] 1,2-diethylpyrazoline-3,5-dione,

[0139] and the addition salts thereof with an acid.

[0140] Among the pyrrolo[3,2-d]oxazole derivatives which may be used asheterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of the compoundsdescribed in patent application JP 07 325 375, the teaching of whichforms an integral part of the present patent application.

[0141] Among the pyrazolo[3,4-d]thiazole derivatives which may be usedas heterocyclic couplers in the dye composition in accordance with theinvention, mention may be made more particularly of compounds describedin patent application JP 07 244 361 and in J. Heterocycl. Chem. 16, 13,(1979).

[0142] Among the thiazoloazole S-oxide and thiazoloazole S,S-dioxidederivatives which may be used as heterocyclic couplers in the dyecomposition in accordance with the invention, mention may be made moreparticularly of the compounds described in the following documents:

[0143] JP 07 098 489;

[0144] Khim. Geterotsilk. Soedin, 1967, p. 93;

[0145] J. Prakt. Chem., 318, 1976, p. 12;

[0146] Indian J. Heterocycl. Chem. 1995, 5 (2), p. 135;

[0147] Acta. Pol. Pharm. 1995, 52 (5), 415;

[0148] Heterocycl. Commun. 1995, 1 (4), 297;

[0149] Arch. Pharm. (Weinheim, Ger.), 1994, 327 (12), 825.

[0150] Among the naphthols and acylated naphthols which may be used ascouplers in the dye composition in accordance with the invention, thecompounds which will preferably be used are those of formula (X) below,and the addition salts thereof with an acid:

[0151] in which:

[0152] R₂₆ represents a hydrogen atom or a group —CO—R in which Rrepresents a C₁-C₄ alkyl radical;

[0153] R₂₇ represents a hydrogen atom, a hydroxyl or C₁-C₄ alkyl radicalor an —SO₃H group;

[0154] R₂₈ represents a hydrogen atom or a hydroxyl radical; it beingunderstood that at least one of the radicals R₂₆ to R₂₈ is other than ahydrogen atom.

[0155] Among the naphthols and acylated naphthols of formula (X) whichmay be used as couplers in the dye composition in accordance with theinvention, mention may be made especially of 1,7-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 2,5-dihydroxynaphthalene,2,3-dihydroxynaphthalene, 1-acetoxy-2-methylnaphthalene,1-hydroxy-2-methylnaphthalene and 1-hydroxy-4-naphthalenesulfonic acid,and the addition salts thereof with an acid.

[0156] When they are present, the coupler(s) preferably represent(s)from 0.0001% to 10% by weight approximately relative to the total weightof the dye composition, and even preferentially from 0.005% to 5% byweight approximately relative to this weight.

[0157] The dye composition in accordance with the invention mayfurthermore also contain at least one additional oxidation base, whichmay be chosen from the oxidation bases conventionally used in oxidationdyeing, and among which mention may be made especially ofpara-phenylenediamines other than the compounds of formula (I) inaccordance with the invention, bis(phenyl)alkylenediamines,para-aminophenols, ortho-aminophenols and heterocyclic bases, and theaddition salts thereof with an acid.

[0158] According to one particular embodiment, the addition base ischosen from heterocyclic oxidation bases, double bases, substitutedpara-aminophenols, ortho-aminophenols, the para-phenylenediaminederivatives of formula (II) below, and the addition salts thereof withan acid:

[0159] in which:

[0160] R₅ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ alkyl radical substitutedwith one or more nitrogenous groups, a phenyl radical or a4′-aminophenyl radical;

[0161] R₆ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radical substitutedwith one or more nitrogenous groups;

[0162] R₇ represents a hydrogen atom, a halogen atom such as a chlorine,bromine, iodine or fluorine atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₁-C₄ hydroxyalkoxy radical, anacetylamino(C₁-C₄)alkoxy radical, a C₁-C₄ mesylaminoalkoxy radical or acarbamoylamino (C₁-C₄) alkoxy radical,

[0163] R₈ represents a hydrogen or halogen atom or a C₁-C₄ alkylradical.

[0164] Among the para-phenylenediamines of formula (II) which can beused as additional oxidation bases in the dye composition in accordancewith the invention, mention may be made more particularly of2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-2-methylaniline,4-amino-2-chloro-N,N-bis(β-hydroxyethyl)aniline,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylenediamine,N,N-dimethyl-3-methyl-para-phenylenediamine,N,N-(ethyl-p-hydroxyethyl)-para-phenylenediamine,N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4′-aminophenyl)-para-phenylenediamine,N-phenyl-para-phenylenediamine,2-β-hydroxy-ethyloxy-para-phenylenediamine,2-β-acetylamino-ethyloxy-para-phenylenediamine andN-(β-methoxyethyl)-para-phenylenediamine, and the addition salts thereofwith an acid.

[0165] Among the para-phenylenediamines of formula (II) above,2-isopropyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-β-hydroxy-ethyloxy-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine,N,N-bis(β-hydroxy-ethyl)-para-phenylenediamine, and2-β-acetylamino-ethyloxy-para-phenylenediamine and the addition saltsthereof with an acid are most particularly preferred.

[0166] Even more preferentially, 2-β-hydroxyethyl-para-phenylenediamine,N,N-bis(β-hydroxyethyl)-para-phenylenediamine, and the addition saltsthereof with an acid, are preferred among the para-phenylenediamines offormula (II) above.

[0167] According to the invention, the term “double bases” is understoodto refer to the compounds containing at least two aromatic rings bearingamino and/or hydroxyl groups.

[0168] Among the double bases which can be used as additional oxidationbases in the dye composition in accordance with the invention, mentionmay be made in particular of the double bases corresponding to formula(III) below, and the addition salts thereof with an acid:

[0169] in which:

[0170] Z₁ and Z₂, which may be identical or different, represent ahydroxyl or —NH₂ radical which may be substituted with a C₁-C₄ alkylradical or with a linker arm Y;

[0171] the linker arm Y represents a linear or branched alkylene chaincontaining from 1 to 14 carbon atoms, which may be interrupted orterminated with one or more nitrogenous groups and/or one or more heteroatoms such as oxygen, sulfur or nitrogen atoms, and optionallysubstituted with one or more hydroxyl or C₁-C₆ alkoxy radicals;

[0172] R₉ and R₁₀ represent a hydrogen or halogen atom, a C₁-C₄ alkylradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ polyhydroxyalkylradical, a C₁-C₄ aminoalkyl radical or a linker arm Y;

[0173] R₁₁, R₁₂, R₁₃, R₁₄, R₁₅ and R₁₆, which may be identical ordifferent, represent a hydrogen atom, a linker arm Y or a C₁-C₄ alkylradical;

[0174] it being understood that the double bases of formula (III)contain only one linker arm Y per molecule.

[0175] Among the nitrogenous groups present in the double base offormula (III) above, mention may be made in particular of amino,mono(C₁-C₄)alkylamino, di(C₁-C₄)alkylamino, tri(C₁-C₄)alkylamino,monohydroxy(C₁-C₄)alkylamino, imidazolinium and ammonium radicals.

[0176] Among the double bases of formula (III) above, mention may bemade more particularly ofN,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)ethylenediamine,N,N′-bis(4-aminophenyl)-tetramethylenediamine,N,N′-bis(β-hydroxyethyl)-N,N′-bis(4-aminophenyl)tetramethylenediamine,N,N′-bis(4-methylaminophenyl)tetramethylenediamine,N,N′-bis(ethyl)-N,N′-bis(4′-amino-3′-methylphenyl)ethylenediamine,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, and the addition saltsthereof with an acid.

[0177] Among these double bases of formula (III),N,N′-bis(β-hydroxyethyl)-N,N′-bis(4′-aminophenyl)-1,3-diaminopropanol,1,8-bis(2,5-diaminophenoxy)-3,5-dioxaoctane, or one of the additionsalts thereof with an acid, are particularly preferred.

[0178] Among the substituted para-aminophenols which can be used assecond oxidation base in the dye composition in accordance with theinvention, mention may be made in particular of the substitutedpara-aminophenols of formula (IV) below, and the addition salts thereofwith an acid:

[0179] in which:

[0180] R₁₇ represents a hydrogen or halogen atom or a C₁-C₄ alkyl, C₁-C₄monohydroxyalkyl, (C₁-C₄)alkoxy(C₁-C₄)-alkyl, C₁-C₄ aminoalkyl orhydroxy(C₁-C₄)-alkylamino (C₁-C₄) alkyl radical,

[0181] R₁₈ represents a hydrogen or halogen atom or a C₁-C₄ alkyl, C₁-C₄monohydroxyalkyl, C₂-C₄ polyhydroxyalkyl, C₁-C₄ aminoalkyl, C₁-C₄cyanoalkyl or (C₁-C₄)alkoxy-(C₁-C₄)alkyl radical,

[0182] it being understood that at least one of the radicals R₁₇ or R₁₈is other than a hydrogen atom.

[0183] Among the para-aminophenols of formula (IV) above, mention may bemade more particularly of para-aminophenol, 4-amino-3-methylphenol,4-amino-3-fluorophenol, 4-amino-3-hydroxymethylphenol,4-amino-2-methylphenol, 4-amino-2-hydroxymethylphenol,4-amino-2-methoxymethylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(p-hydroxyethylaminomethyl)phenol, 4-amino-2-fluorophenol, andthe addition salts thereof with an acid.

[0184] Among the ortho-aminophenols which can be used as additionaloxidation bases in the dye compositions in accordance with theinvention, mention may be made more particularly of 2-aminophenol,2-amino-5-methylphenol, 2-amino-6-methylphenol and5-acetamido-2-aminophenol, and the addition salts thereof with an acid.

[0185] Among the heterocyclic bases which can be used as oxidation basesin the dye compositions in accordance with the invention, mention may bemade more particularly of pyridine derivatives, pyrimidine derivatives,pyrazole derivatives, and the addition salts thereof with an acid.

[0186] Among the pyridine derivatives, mention may be made moreparticularly of the compounds described, for example, in patents GB 1026 978 and GB 1 153 196, such as 2,5-diaminopyridine,2-(4-methoxyphenyl)amino-3-aminopyridine, 2,3-diamino-6-methoxypyridine,2-(β-methoxyethyl)amino-3-amino-6-methoxypyridine and3,4-diaminopyridine, and the addition salts thereof with an acid.

[0187] Among the pyrimidine derivatives, mention may be made moreparticularly of the compounds described, for example, in German patentDE 2 359 399 or Japanese patents JP 88-169 571 and JP 05 163 124;European Patent 0 770 375 or patent application WO 96/15765, such as2,4,5,6-tetramino-pyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine,2-hydroxy-4,5,6-triaminopyrimidine, 6-hydroxy-2,4,5-triaminopyrimidine2,4-dihydroxy-5,6-diaminopyrimidine, 2,5,6-triaminopyrimidine andpyrazolopyrimidine derivatives such as those mentioned in patentapplication FR-A-2 750 048, and among which mention may be made ofpyrazolo[1,5-a]pyrimidine-3,7-diamine;2,5-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine;pyrazolo[1,5-a]pyrimidine-3,5-diamine;2,7-dimethylpyrazolo[1,5-a]pyrimidine-3,5-diamine;3-aminopyrazolo[1,5-a]pyrimidin-7-ol;3-aminopyrazolo[1,5-a]pyrimidin-5-ol;2-(3-aminopyrazolo[1,5-a]pyrimidin-7-ylamino)ethanol;2-(7-aminopyrazolo[1,5-a]pyrimidin-3-ylamino)ethanol,2-[(3-aminopyrazolo[1,5-a]pyrimidin-7-yl)-(2-hydroxyethyl)amino]ethanol,2-[(7-amino-pyrazol[1,5-a]pyrimidin-3-yl)-(2-hydroxyethyl)amino]-ethanol,5,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,2,6-dimethylpyrazolo[1,5-a]pyrimidine-3,7-diamine,2,5,N7,N7-tetramethylpyrazolo[1,5-a-[pyrimidine-3,7-diamine,3-amino-5-methyl-7-imidazolylpropylaminopyrazolo[1,5-a]pyrimidine, theaddition salts thereof with an acid, and the tautomeric forms thereof,when a tautomeric equilibrium exists.

[0188] Among the pyrazole derivatives, mention may be made moreparticularly of the compounds described in patents DE 3 843 892, DE 4133 957 and patent applications WO 94/08969, WO 94/08970, FR-A-2 733 749and DE 195 43 988, such as 4,5-diamino-1-methylpyrazole,3,4-diaminopyrazole, 4,5-diamino-1-(4′-chlorobenzyl)pyrazole,4,5-diamino-1,3-dimethyl-pyrazole,4,5-diamino-1-(β-hydroxyethyl)pyrazole4,5-diamino-3-methyl-1-phenylpyrazole,4,5-diamino-1-methyl-3-phenylpyrazole,4-amino-1,3-dimethyl-5-hydrazinopyrazole,1-benzyl-4,5-diamino-3-methylpyrazole,4,5-diamino-3-tert-butyl-1-methylpyrazole,4,5-diamino-1-tert-butyl-3-methylpyrazole,4,5-diamino-1-(β-hydroxyethyl)-3-methylpyrazole,4,5-diamino-1-ethyl-3-methylpyrazole,4,5-diamino-1-ethyl-3-(4′-methoxyphenyl)pyrazole,4,5-diamino-1-ethyl-3-hydroxymethylpyrazole,4,5-diamino-3-hydroxymethyl-1-methylpyrazole,4,5-diamino-3-hydroxymethyl-1-isopropylpyrazole,4,5-diamino-3-methyl-1-isopropylpyrazole,4-amino-5-(2′-aminoethyl)amino-1,3-dimethylpyrazole,3,4,5-triaminopyrazole, 1-methyl-3,4,5-triaminopyrazole,3,5-diamino-1-methyl-4-methylaminopyrazole and3,5-diamino-4-(β-hydroxyethyl)amino-1-methylpyrazole, and the additionsalts thereof with an acid.

[0189] When they are used, the additional oxidation base(s) preferablyrepresent(s) from 0.0005% to 12% by weight approximately relative to thetotal weight of the dye composition, and even more preferentially from0.005% to 6% by weight approximately relative to this weight.

[0190] In general, the addition salts with an acid which may be used inthe context of the dye compositions of the invention (compounds offormula (I), couplers and additional oxidation bases) are chosenespecially from the hydrochlorides, hydrobromides, sulfates, citrates,succinates, tartrates, lactates, phosphates and acetates.

[0191] The dye composition in accordance with the invention may alsocontain one or more direct dyes. This direct dye may be a syntheticdirect dye chosen from azo dyes, quinone dyes, triarylmethane dyes,indoamine dyes and azine dyes and/or a natural dye. The synthetic directdyes which may be used according to the invention may be nonionic,anionic or cationic.

[0192] Among the synthetic azo direct dyes which may be used accordingto the invention, mention may be made of cationic azo dyes described inpatent applications WO 95/15144, WO 95/01772 and EP-714 954, the contentof which forms an integral part of the invention.

[0193] Among the azo direct dyes, mention may also be made of thefollowing dyes, described in the Colour Index International 3rd edition:Disperse Red 17, Acid Yellow 9, Acid Black 1, Basic Red 22, Basic Red76, Basic Yellow 57, Basic Brown 16, Acid Yellow 36, Acid Orange 7, AcidRed 33, Acid Red 35, Basic Brown 17, Acid Yellow 23, Acid Orange 24,Disperse Black 9. Among these, mention may also be made of1-(4′-aminodiphenyl-azo)-2-methyl-4-bis(β-hydroxyethyl)aminobenzene and4-hydroxy-3-(2-methoxyphenylazo)-1-naphthalene sulfonic acid.

[0194] Among the synthetic quinone direct dyes, mention may be made ofthe following: Disperse Red 15, Solvent Violet 13, Acid Violet 43,Disperse Violet 1, Disperse Violet 4, Disperse Blue 1, Disperse Violet8, Disperse Blue 3, Disperse Red 11, Acid Blue 62, Disperse Blue 7,Basic Blue 22, Disperse Violet 15, Basic Blue 99, and also thecompounds:

[0195] 1-N-methylmorpholiniumpropylamino-4-hydroxyanthraquinone,

[0196] 1-aminopropylamino-4-methylaminoanthraquinone,

[0197] 1-aminopropylaminoanthraquinone,

[0198] 5-β-hydroxyethyl-1,4-diaminoanthraquinone,

[0199] b 2-aminomethylaminoanthraquinone,

[0200] 1,4-bis(β,γ-dihydroxypropylamino)anthraquinone.

[0201] Among the synthetic azine direct dyes, mention may be made of thefollowing: Basic Blue 17, Basic Red 2.

[0202] Among the synthetic triarylmethane direct dyes which may be usedaccording to the invention, mention may be made of the following: BasicGreen 1, Acid Blue 9, Basic Violet 3, Basic Violet 14, Basic Blue 7,Acid Violet 49, Basic Blue 26, Acid Blue 7.

[0203] Among the synthetic indoamine direct dyes which may be usedaccording to the invention, mention may be made of the following:

[0204]2-β-hydroxyethylamino-5-[bis(β-4′-hydroxyethyl)-amino]anilino-1,4-benzoquinone

[0205]2-β-hydroxyethylamino-5-(2′-methoxy-4′-amino)anilino-1,4-benzoquinone

[0206]3-N-(2′-chloro-4′-hydroxy)phenylacetylamino-6-methoxy-1,4-benzoquinoneimine

[0207]3-N-(3′-chloro-4′-methylamino)phenylureido-6-methyl-1,4-benzoquinoneimine

[0208]3-[4′-N-(ethylcarbamylmethyl)amino]phenylureido-6-methyl-1,4-benzoquinoneimine.

[0209] For the purposes of the invention, the term “natural dye” meanscompounds which exist in nature, whether they have been obtained byextraction or reproduced chemically. Among the natural direct dyes whichmay be used according to the invention, mention may be made of lawsone,juglone, alizarin, purpurine, carminic acid, kermesic acid,purpurogallin, protocatechaldehyde, indigo, isatin, curcumin, spinulosinand apigenidin. Extracts or decoctions containing these natural dyes,and especially henna-based poultices or extracts, may also be used.

[0210] The synthetic direct dye(s) according to the invention and/or thenatural dye(s) represent(s) from 0.001% to-20% by weight approximatelyrelative to the total weight of the composition, and even morepreferentially from 0.005% to 10% by weight approximately.

[0211] The dye composition in accordance with the invention may alsocontain various adjuvants conventionally used in compositions for dyeingthe hair, such as anionic, cationic, nonionic, amphoteric orzwitterionic surfactants or mixtures thereof, anionic, cationic,nonionic, amphoteric or zwitterionic polymers or mixtures thereof,mineral or organic thickeners, antioxidants, penetration agents,sequestering agents, fragrances, buffers, dispersants, conditioners suchas, for example, volatile or non-volatile silicones, modified orunmodified silicones, film-forming agents, ceramides, preserving agentsand opacifiers.

[0212] According to one particular embodiment, the dye composition ofthe invention comprises at least one polymer chosen from:

[0213] (i) amphoteric polymers,

[0214] (ii) cationic polymers containing repeating units of structures(II) or (III) below, and

[0215] (iii) polymers other than the above, which are amphiphilic andcomprise at least one fatty chain,

[0216] Structure (II):

[0217] in which:

[0218] R₅, R₆, R₇ and R₈, which may be identical or different, representaliphatic, alicyclic or arylaliphatic radicals containing from 1 to 20carbon atoms or lower hydroxyalkylaliphatic radicals, or alternativelyR₅, R₆, R₇ and R₈, together or separately, constitute, with the nitrogenatoms to which they are attached, heterocycles optionally containing asecond heteroatom other than nitrogen, or alternatively R₅, R₆, R₇ andR₈ represent a linear or branched C₁-C₆ alkyl radical substituted with anitrile, ester, acyl, amide or —CO—O—R₁₃—D or —CO—NH—R₁₃—D group inwhich R₁₃ is an alkylene and D is a quaternary ammonium group;

[0219] A₁ and B₁ represent polymethylene groups containing from 2 to 20carbon atoms which may be linear or branched, saturated or unsaturatedand which may contain, linked to or intercalated in the main chain, oneor more aromatic rings, or one or more oxygen or sulfur atoms orsulfoxide, sulfone, disulfide, amino, alkylamino, hydroxyl, quaternaryammonium, ureido, amide or ester groups.

[0220] A₁, R₅ and R₇ may form with the two nitrogen atoms to which theyare attached a piperazine ring; in addition, if A₁ denotes a linear orbranched, saturated or unsaturated alkylene or hydroxyalkylene radical,B₁ can also denote a group —(CH₂)_(n)—CO—T—OC—(CH₂)_(n)— in which n isbetween 1 and 100 and preferably between 1 and 50, and T denotes:

[0221] a) a glycol residue of formula: —O—Z—O—, in which Z denotes alinear or branched hydrocarbon-based radical or a group corresponding toone of the following formulae:

—(CH₂—CH₂—O)x-CH₂—CH₂—

—[CH₂—CH(CH₃)—O]y-CH₂—CH(CH₃)—

[0222] in which x and y denote an integer from 1 to 4, representing adefined and unique degree of polymerization, or any number from 1 to 4representing an average degree of polymerization;

[0223] b) a bis-secondary diamine residue such as a piperazinederivative;

[0224] c) a bis-primary diamine residue of formula: —NH—Y—NH—, in whichY denotes a linear or branched hydrocarbon-based radical, oralternatively the divalent radical

—CH₂—CH₂—S—S—CH₂—CH₂—;

[0225] d) a ureylene group of formula: —NH—CO—NH—;

[0226] X₁ ⁻ is an anion derived from a mineral or organic acid andpreferably chlorine or bromine;

[0227] Structure (III)

[0228] in which:

[0229] R₉, R₁₀, R₁₁ and R₁₂, which may be identical or different,represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl,β-hydroxypropyl or —CH₂CH₂(OCH₂CH₂)pOH radical, in which p is equal to 0or to an integer between 1 and 6,

[0230] with the proviso that R₉, R₁₀, R₁₁ and R₁₂ do not simultaneouslyrepresent a hydrogen atom,

[0231] r and s, which may be identical or different, are integersbetween 1 and 6,

[0232] D is zero or denotes a group —(CH₂)_(q)—CO— in which q is zero orequal to an integer between 1 and 34,

[0233] A denotes a dihalide radical or, preferably, represents—CH₂—CH₂—O—CH₂—CH₂—,

[0234] X₂ ⁻ denotes an anion derived from a mineral or organic acid,preferably a halogen atom.

[0235] The cationic polymers containing repeating units of structure(II) preferably have a number-average molecular mass generally between 1000 and 100 000.

[0236] Polymers of this type are especially described in French patents2 320 330, 2 270 846, 2 316 271, 2 336 434 and 2 413 907 and U.S. Pat.Nos. 2,273,780, 2,375,853, 2,388,614, 2,454,547, 3,206,462, 2,261,002,2,271,378, 3,874,870, 4,001,432, 3,929,990, 3,966,904, 4,005,193,4,025,617, 4,025,627, 4,025,653, 4,026,945 and 4,027,020.

[0237] According to the invention, among these cationic polymerscontaining units of structure (II), those more particularly used arethose consisting of repeating units corresponding to structure (IV)below:

[0238] in which R₁₄, R₁₅, R₁₆ and R₁₇, which may be identical ordifferent, denote an alkyl or hydroxyalkyl radical containing from 1 to4 carbon atoms approximately, n and p are integers ranging from 2 to 20approximately, and X₃ ⁻ is an anion derived from a mineral or organicacid.

[0239] More particularly, it is also preferred to use the polymercontaining units of structure (IV) in which R₁₄, R₁₅, R₁₆ and R₁₇ denotea methyl radical, n and p are equal to 6 and 3, respectively, and X₃ ⁻is equal to Cl⁻; this polymer has the INCI name: HexadimethrineChloride.

[0240] The cationic polymers containing repeating units of structure(III) are especially described in patent application EP-A-122 324 andmay be prepared according to the processes described in U.S. Pat. Nos.4,157,388, 4,390,689, 4,702,906 and 4,719,282.

[0241] Among these polymers, it is more particularly preferred accordingto the invention to use those consisting of repeating unitscorresponding to structure (V) below:

—[—N⁺(CH₃)₂—(CH₂)_(r)—NH—CO—D—NH—(CH₂)_(r)—N⁺(CH₃)₂—(CH₂)₂—O—(CH₂)₂]-2X⁻  (V)

[0242] in which r denotes an integer ranging from 1 to 6 approximately,D may be 0 or may represent a group —(CH₂)_(q)—CO— in which q denotes anumber equal to 4 or to 7, and X⁻ is an anion derived from a mineral ororganic acid, and preferably with a molecular mass, measured bycarbon-13 NMR, of less than 100 000.

[0243] Among the cationic polymers of structure (V) which are even moreparticularly preferred are those for which:

[0244] a) D represents a group —(CH₂)₄—CO—, X denotes a chlorine atom,the molecular mass, measured by carbon-13 NMR (C¹³ NMR), being about 5600; a polymer of this type is proposed by the company Miranol under thename Mirapol-AD1,

[0245] b) D represents a group —(CH₂)₇—CO— and X denotes a chlorineatom, the molecular mass, measured by carbon-13 NMR (C¹³NMR) being about8100; a polymer of this type is proposed by the company Miranol underthe name Mirapol-AZ1,

[0246] c) D denotes the value zero and X denotes a chlorine atom, themolecular mass, measured by carbon-13 NMR (C¹³ NMR), being about 25 500;a polymer of this type is sold by-the company Miranol under the nameMirapol-A15,

[0247] d) a “block copolymer” formed from units corresponding to thepolymers described in paragraphs a) and c), sold by the company Miranolunder the names Mirapol-9 (C¹³ NMR molecular mass of about 7 800)Mirapol-175 (C¹³ NMR molecular mass of about 8 000) and Mirapol-95 (C¹³NMR molecular mass of about 12 500).

[0248] Even more particularly, the polymer which is preferred accordingto the invention is the polymer of formula (V) in which D denotes thevalue zero, X denotes a chlorine atom, the molecular mass, measured bycarbon-13 NMR (C¹³ NMR), being about 25 500.

[0249] According to the invention, the cationic polymer(s) can representfrom 0.01% to 10% by weight approximately relative to the total weightof the composition, preferably from 0.05% to 5% and even morepreferentially from 0.1% to 3%.

[0250] The amphoteric polymers which can be used in accordance with thepresent invention can be chosen from polymers containing units K and Mdistributed randomly in the polymer chain, in which K denotes a unitderived from a monomer containing at least one basic nitrogen atom and Mdenotes a unit derived from an acid monomer containing one or morecarboxylic or sulfonic groups, or alternatively K and M can denotegroups derived from carboxybetaine or sulfobetaine zwitterionicmonomers;

[0251] K and M can also denote a cationic polymer chain containingprimary, secondary, tertiary or quaternary amine groups, in which atleast one of the amine groups bears a carboxylic or sulfonic groupconnected via a hydrocarbon-based radical, or alternatively K and M formpart of a chain of a polymer containing an α,β-dicarboxylic ethyleneunit in which one of the carboxylic groups has been made to react with apolyamine containing one or more primary or secondary amine groups.

[0252] The amphoteric polymers which are more particularly preferred arechosen from the following polymers:

[0253] (1) Polymers resulting from the copolymerization of a monomerderived from a vinyl compound bearing a carboxylic group such as, moreparticularly, acrylic acid, methacrylic acid, maleic acid,α-chloroacrylic acid, and a basic monomer derived from a substitutedvinyl compound containing at least one basic atom, such as, moreparticularly, dialkylaminoalkyl methacrylates and acrylates,dialkylaminoalkylmethacrylamides and -acrylamides. Such compounds aredescribed in U.S. Pat. No. 3,836,537. Mention may also be made of thesodium acrylate/acrylamidopropyltrimethylammonium chloride copolymersold under the name Polyquart KE 3033 by the company Henkel.

[0254] The substituted vinyl compound which contains at least one basicatom can also be a dialkyldiallylammonium salt such asdimethyldiallylammonium chloride. The copolymers of acrylic acid and ofthe latter monomer are sold under the names Merquat 280, Merquat 295 andMerquat Plus 3330 by the company Calgon.

[0255] (2) Polymers containing units derived from:

[0256] a) at least one monomer chosen from acrylamides andmethacrylamides substituted on the nitrogen with an alkyl radical,

[0257] b) at least one acidic comonomer containing one or more reactivecarboxylic groups, and

[0258] c) at least one basic comonomer such as esters containingprimary, secondary, tertiary and quaternary amine substituents ofacrylic and methacrylic acids and the product of quaternization ofdimethylaminoethyl methacrylate with dimethyl or diethyl sulfate.

[0259] The N-substituted acrylamides or methacrylamides which are moreparticularly preferred according to the invention are groups in whichthe alkyl radicals contain from 2 to 12 carbon atoms and moreparticularly N-ethylacrylamide, N-tert-butylacrylamide,N-tert-octylacrylamide, N-octylacrylamide, N-decylacrylamide,N-dodecylacrylamide and the corresponding methacrylamides.

[0260] The acidic comonomers are chosen more particularly from acrylicacid, methacrylic acid, crotonic acid, itaconic acid, maleic acid,fumaric acid and alkyl monoesters, having 1 to 4 carbon atoms, or maleicor fumaric acids or anhydrides.

[0261] The preferred basic comonomers are aminoethyl, butylaminoethyl,N,N′-dimethylaminoethyl and N-tert-butylaminoethyl methacrylates.

[0262] The copolymers whose CTFA (4th edition, 1991) name isoctylacrylamide/acrylates/butylaminoethyl methacrylate copolymer such asthe products sold under the name Amphomer or Lovocryl 47 by the companyNational Starch are particularly used.

[0263] (3) Crosslinked and alkylated polyamino amides partially ortotally derived from polyamino amides of general formula:

CO—R—CO—Z  (VI)

[0264] in which R₁₈ represents a divalent radical derived from asaturated dicarboxylic acid, a mono- or dicarboxylic aliphatic acidcontaining an ethylenic double bond, an ester of a lower alkanol, having1 to 6 carbon atoms of these acids or a radical derived from theaddition of any one of said acids to a bis(primary) or bis(secondary)amine, and Z denotes a bis(primary), mono- or bis(secondary)polyalkylene-polyamine radical and preferably represents:

[0265] a) in proportions of from 60 to 100 mol %, the radical

[0266] where x=2 and p=2 or 3, or alternatively x=3 and p=2

[0267] this radical being derived from diethylenetriamine, fromtriethylenetetraamine or from dipropylenetriamine;

[0268] b) in proportions of from 0 to 40 mol %, the radical (VII) above,in which x=2 and p=1 and which is derived from ethylenediamine, or theradical derived from piperazine:

[0269] c) in proportions of from 0 to 20 mol %, the —NH—(CH₂)₆—NH—radical derived from hexamethylene-diamine, these polyamino amines beingcrosslinked by addition of a difunctional crosslinking agent chosen fromepihalohydrins, diepoxides, dianhydrides and bis-unsaturatedderivatives, using from 0.025 to 0.35 mol of crosslinking agent peramine group of the polyamino amide and alkylated by the action ofacrylic acid, chloroacetic acid or an alkane sultone, or salts thereof.

[0270] The saturated carboxylic acids are preferably chosen from acidshaving 6 to 10 carbon atoms, such as adipic acid, 2,2,4-trimethyladipicacid and 2,4,4-trimethyladipic acid, terephthalic acid, acids containingan ethylenic double bond such as, for example, acrylic acid, methacrylicacid and itaconic acid.

[0271] The alkane sultones used in the alkylation are preferably propanesultone or butane sultone, the salts of the alkylating agents arepreferably the sodium or potassium salts.

[0272] (4) Polymers containing zwitterionic units of formula:

[0273] in which R₂₃ denotes a polymerizable unsaturated group such as anacrylate, methacrylate, acrylamide or methacrylamide group, y and zrepresent an integer from 1 to 3, R₁₉ and R₂₀ represent a hydrogen atom,methyl, ethyl or propyl, R₂₁ and R₂₂ represent a hydrogen atom or analkyl radical such that the sum of the carbon atoms in R₂₁ and R₂₂ doesnot exceed 10.

[0274] The polymers comprising such units can also contain units derivedfrom non-zwitterionic monomers such as dimethyl or diethylaminoethylacrylate or methacrylate or alkyl acrylates or methacrylates,acrylamides or methacrylamides or vinyl acetate.

[0275] By way of example, mention may be made of the copolymer of butylmethacrylate/dimethyl carboxymethylammonio ethyl methacrylate such asthe product sold under the name Diaformer Z301 by the company Sandoz.

[0276] (5) Polymers derived from chitosan containing monomer unitscorresponding to the following formulae (IX), (X) and (XI):

[0277] the unit (IX) being present in proportions of between 0 and 30%,the unit (X) in proportions of between 5 and 50% and the unit (XI) inproportions of between 30 and 90%, it being understood that, in thisunit (XI), R₂₄ represents a radical of formula:

[0278] in which

[0279] if q=0, R₂₅, R₂₆ and R₂₇, which may be identical or different,each represent a hydrogen atom, a methyl, hydroxyl, acetoxy or aminoresidue, a monoalkylamine residue or a dialkylamine residue which areoptionally interrupted by one or more nitrogen atoms and/or optionallysubstituted with one or more amine, hydroxyl, carboxyl, alkylthio orsulfonic groups, an alkylthio residue in which the alkyl group bears anamino residue, at least one of the radicals R₂₅, R₂₆ and R₂₇ being, inthis case, a hydrogen atom;

[0280] or, if q 1, R₂₅, R₂₆ and R₂₇ each represent a hydrogen atom, aswell as the salts formed by these compounds with bases or acids.

[0281] (6) Polymers derived from the N-carboxyalkylation of chitosan,such as N-carboxymethylchitosan or N-carboxybutylchitosan sold under thename “Evalsan” by the company Jan Dekker.

[0282] (7) Polymers corresponding to the general formula (XII) aredescribed, for example, in French patent 1 400 366:

[0283] in which R₃₂ represents a hydrogen atom, a CH₃O, CH₃CH₂O orphenyl radical, R₂₈ denotes hydrogen or a lower alkyl radical such asmethyl or ethyl, R₂₉ denotes hydrogen or a lower alkyl radical such asmethyl or ethyl, R₃₀ denotes a lower alkyl radical such as methyl orethyl or a radical corresponding to the formula: —R₃₁—N(R₂₉)₂, R₃₁representing a —CH₂—CH₂—, —CH₂—CH₂—CH₂— or —CH₂—CH(CH₃)— group, R₂₉having the meanings mentioned above,

[0284] as well as the higher homologs of these radicals and containingup to 6 carbon atoms.

[0285] r is such that the molecular weight is between 500 and 6 000 000and preferably between 1 000 and 1 000 000.

[0286] (8) Amphoteric polymers of the type —D—X—D—X chosen from:

[0287] a) polymers obtained by the action of chloroacetic acid or sodiumchloroacetate on compounds containing at least one unit of formula:

—D—X—D—X—D—  (XIII)

[0288] where D denotes a radical

[0289] and X denotes the symbol E or E′. E or E′, which may be identicalor different, denote a divalent radical which is an alkylene radicalcontaining a straight or branched chain containing up to 7 carbon atomsin the main chain, which is unsubstituted or substituted with hydroxylgroups and which can contain, in addition to the oxygen, nitrogen andsulfur atoms, 1 to 3 aromatic and/or heterocyclic rings; the oxygen,nitrogen and sulfur atoms being present in the form of ether, thioether,sulfoxide, sulfone, sulfonium, alkylamine or alkenylamine groups,hydroxyl, benzylamine, amine oxide, quaternary ammonium, amide, imide,alcohol, ester and/or urethane groups.

[0290] b) polymers of formula:

—D—X—D—X—  (XIV)

[0291] in which D denotes a radical

[0292] and X denotes the symbol E or E′ and at least once E′; E havingthe meaning given above and E′ is a divalent radical which is analkylene radical with a straight or branched chain having up to 7 carbonatoms in the main chain, which is unsubstituted or substituted with oneor more hydroxyl radicals and containing one or more nitrogen atoms, thenitrogen atom being substituted with an alkyl chain which is optionallyinterrupted by an oxygen atom and necessarily containing one or morecarboxyl functions or one or more hydroxyl functions and betainized byreaction with chloroacetic acid or sodium chloroacetate.

[0293] (9) (C₁-C₅)alkyl vinyl ether/maleic anhydride copolymerspartially modified by semiamidation with an N,N-dialkylaminoalkylaminesuch as N,N-dimethylaminopropylamine or by semiesterification with anN,N-dialkanolamine. These copolymers can also contain other vinylcomonomers such as vinylcaprolactam.

[0294] The amphoteric polymers which are particularly preferredaccording to the invention are those of family (1).

[0295] According to the invention, the amphoteric polymer(s) canrepresent from 0.01% to 10% by weight, preferably from 0.05% to 5% byweight and even more preferably from 0.1% to 3% by weight, relative tothe total weight of the composition.

[0296] The polymers other than the above which are amphiphilic andcontain at least one fatty chain, which are useful in the presentinvention, are also known as associative polymers; they may be ofnonionic, anionic or cationic type.

[0297] Among the amphiphilic polymers comprising at least one fattychain and of anionic type, mention may be made of:

[0298] (I) those comprising at least one hydrophilic unit and at leastone allyl ether unit containing a fatty chain, more particularly thoseof which the hydrophilic unit consists of an ethylenic unsaturatedanionic monomer, even more particularly a vinylcarboxylic acid and mostparticularly an acrylic acid, a methacrylic acid or mixtures thereof,the allyl ether unit containing a fatty chain corresponding to themonomer of formula (XV) below:

CH₂═CR′CH₂OB_(n)R  (XV)

[0299] in which R′ denotes H or CH₃, B denotes an ethyleneoxy radical, nis zero or denotes an integer ranging from 1 to 100, R denotes ahydrocarbon-based radical chosen from alkyl, arylalkyl, aryl, alkylaryland cycloalkyl radicals, containing 8 to 30 carbon atoms, preferably 10to 24 carbon atoms and even more particularly from 12 to 18 carbonatoms. A unit of formula (XV) which is more particularly preferred is aunit in which R′ denotes H, n is equal to 10 and R denotes a stearyl(C₁₈) radical.

[0300] Anionic amphiphilic polymers of this type are described andprepared, according to an emulsion polymerization process, in patentEP-0 216 479.

[0301] Among these fatty-chain anionic polymers, those which areparticularly preferred according to the invention are polymers formedfrom 20% to 60% by weight of acrylic acid and/or of methacrylic acid,from 5% to 60% by weight of lower alkyl (meth)acrylates, from 2% to 50%by weight of allyl ether containing a fatty chain of formula (XV), andfrom 0% to 1% by weight of a crosslinking agent which is a well-knowncopolymerizable unsaturated polyethylenic monomer, for instance diallylphthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycoldimethacrylate or methylenebisacrylamide.

[0302] Among the latter polymers, those most particularly preferred arecrosslinked terpolymers of methacrylic acid, of ethyl acrylate and ofpolyethylene glycol (10 EO) stearyl ether (Steareth-10), in particularthose sold by the company Allied Colloids under the names Salcare SC 80and Salcare SC 90, which are aqueous 30% emulsions of a crosslinkedterpolymer of methacrylic acid, of ethyl acrylate and of steareth-10allyl ether (40/50/10).

[0303] (II) those comprising at least one hydrophilic unit ofunsaturated olefinic carboxylic acid type, and at least one hydrophobicunit of (C₁₀-C₃₀)alkyl ester of unsaturated carboxylic acid type.

[0304] Preferably, these polymers are chosen from those in which thehydrophilic unit of unsaturated olefinic carboxylic acid typecorresponds to the monomer of formula (XVI) below:

[0305] in which R₁ denotes H or CH₃ or C₂H₅, that is to say acrylicacid, methacrylic acid or ethacrylic acid units, and in which thehydrophobic unit of (C₁₀-C₃₀)alkyl ester of unsaturated carboxylic acidtype corresponds to the monomer of formula (XVII) below:

[0306] in which R₂ denotes H or CH₃ or C₂H₅ (that is to say acrylate,methacrylate or ethacrylate units) and preferably H (acrylate units) orCH₃ (methacrylate units), R₃ denoting a C₁₀-C₃₀ and preferably C₁₂-C₂₂alkyl radical.

[0307] (C₁₀-C₃₀) alkyl esters of unsaturated carboxylic acids accordingto the invention include, for example, lauryl acrylate, stearylacrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, andthe corresponding methacrylates, lauryl methacrylate, stearylmethacrylate, decyl methacrylate, isodecyl methacrylate and dodecylmethacrylate.

[0308] Anionic polymers of this type are described and prepared, forexample, according to U.S. Pat. Nos. 3,915,921 and 4,509,949.

[0309] Among the fatty-chain anionic polymers of this type which will beused more particularly are polymers formed from a monomer mixturecomprising:

[0310] (i) essentially acrylic acid,

[0311] (ii) an ester of formula (XVI) described above in which R₂denotes H or CH₃, R₃ denoting an alkyl radical containing from 12 to 22carbon atoms,

[0312] (iii) and a crosslinking agent, which is a well-knowncopolymerizable polyethylenic unsaturated monomer, for instance diallylphthalate, allyl (meth)acrylate, divinylbenzene, (poly)ethylene glycoldimethacrylate and methylenebisacrylamide.

[0313] Among fatty-chain anionic polymers of this type which will beused more particularly are those consisting of from 95% to 60% by weightof acrylic acid (hydrophilic unit), 4% to 40% by weight of C₁₀-C₃₀ alkylacrylate (hydrophobic unit) and 0% to 6% by weight of crosslinkingpolymerizable monomer, or alternatively those consisting of from 98% to96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight ofC₁₀-C₃₀ alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight ofcrosslinking polymerizable monomer such as those described above.

[0314] Among said above polymers, those most particularly preferredaccording to the present invention are the products sold by the companyGoodrich under the trade names Pemulen TR1, Pemulen TR2 and Carbopol1382, and even more preferentially Pemulen TR1, and the product sold bythe company S.E.P.P.I.C under the name Coatex SX.

[0315] (III) maleic anhydride/C₃₀-C₃₈ α-olefin/alkyl maleateterpolymers, such as the product (maleic anhydride/C₃₀-C₃₈α-olefin/isopropyl maleate copolymer) sold under the name Performa V1608 by the company Newphase Technologies.

[0316] (IV) acrylic terpolymers comprising:

[0317] (a) about 20% to 70% by weight of a carboxylic acid containingα,β-monoethylenic unsaturation,

[0318] (b) about 20% to 80% by weight of a non-surfactant monomercontaining α,β-monoethylenic unsaturation other than (a),

[0319] (c) about 0.5% to 60% by weight of a nonionic monourethane whichis the product of reaction of a monohydric surfactant with amonoisocyanate containing monoethylenic unsaturation, such as thosedescribed in patent application EP-A-0 173 109 and more particularly theterpolymer described in example 3, namely a methacrylic acid/methylacrylate/behenyl dimethyl-meta-isopropenylbenzylisocyanate ethoxylated(40 EO) terpolymer, as an aqueous 25% dispersion.

[0320] (V) copolymers comprising among their monomers a carboxylic acidcontaining α,β-monoethylenic unsaturation and an ester of a carboxylicacid containing α,β-monoethylenic unsaturation and of a(C₈-C₃₀)oxyalkylenated fatty alcohol.

[0321] Preferentially, these compounds also comprise as monomer an esterof a carboxylic acid containing α,β-monoethylenic unsaturation and of aC₁-C₄ alcohol.

[0322] An example of a compound of this type which may be mentioned isAculyn 22 sold by the company Rohm & Haas, which is a methacrylicacid/ethyl acrylate/stearyl methacrylate oxyalkylenated terpolymer.

[0323] The fatty-chain amphiphilic polymers of nonionic type which areused according to the invention are preferably chosen from:

[0324] (1) celluloses modified with groups comprising at least one fattychain;

[0325] examples which may be mentioned include:

[0326] hydroxyethylcelluloses modified with groups comprising at leastone fatty chain, such as alkyl, arylalkyl or alkylaryl groups, ormixtures thereof, and in which the alkyl groups are preferably C₈-C₂₂,for instance the product Natrosol Plus Grade 330 CS(C₁₆ alkyls) sold bythe company Aqualon, or the product Bermocoll EHM 100 sold by thecompany Berol Nobel.

[0327] those modified with alkylphenyl polyalkylene glycol ether groups,such as the product Amercell Polymer HM-1500 (nonylphenyl polyethyleneglycol (15) ether) sold by the company Amerchol.

[0328] (2) hydroxypropylguars modified with groups comprising at leastone fatty chain, such as the product Esaflor HM 22 (C₂₂ alkyl chain)sold by the company Lamberti, and the products RE210-18 (C₁₄ alkylchain) and RE205-1 (C₂₀ alkyl chain) sold by the company Rhône-Poulenc.

[0329] (3) copolymers of vinylpyrrolidone and of fatty-chain hydrophobicmonomers;

[0330] examples which may be mentioned include:

[0331] the products Antaron V216 or Ganex V216(vinylpyrrolidone/hexadecene copolymer) sold by the company I.S.P

[0332] the products Antaron V220 or Ganex V220(vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P.

[0333] (4) copolymers of C₁-C₆ alkyl methacrylates or acrylates and ofamphiphilic monomers comprising at least one fatty chain, such as, forexample, the oxyethylenated methyl acrylate/stearyl acrylate copolymersold by the company Goldschmidt under the name Antil 208.

[0334] (5) copolymers of hydrophilic methacrylates or acrylates and ofhydrophobic monomers comprising at least one fatty chain, such as, forexample, the polyethylene glycol methacrylate/lauryl methacrylatecopolymer.

[0335] (6) polymers with an aminoplast ether skeleton containing atleast one fatty chain, such as the Pure Thix compounds sold by thecompany Sud-Chemie.

[0336] (7) polyurethane polyethers comprising in their chain bothhydrophilic blocks usually of polyoxyethylenated nature and hydrophobicblocks which may be aliphatic sequences alone and/or cycloaliphaticand/or aromatic sequences,

[0337] Preferably, the polyether polyurethanes comprising at least twohydrocarbon-based lipophilic chains containing from 6 to 30 carbonatoms, separated by a hydrophilic block, the hydrocarbon-based chainspossibly being pendent chains, or chains at the end of the hydrophilicblock. In particular, it is possible for one or more pendent chains tobe included. In addition, the polymer may comprise a hydrocarbon-basedchain at one end or at both ends of a hydrophilic block.

[0338] The polyether polyurethanes may be multiblock, in particular intriblock form. Hydrophobic blocks may be at each end of the chain (forexample: triblock copolymer with a hydrophilic central block) ordistributed both at the ends and in the chain (for example: multiblockcopolymer). These same polymers may also be graft polymers or starburstpolymers.

[0339] The nonionic fatty-chain polyether polyurethanes may be triblockcopolymers in which the hydrophilic block is a polyoxyethylenated chaincomprising from 50 to 1 000 oxyethylene groups. The nonionic polyetherpolyurethanes comprise a urethane linkage between the hydrophilicblocks, whence arises the name.

[0340] By extension, also included among the nonionic fatty-chainpolyether polyurethanes are those in which the hydrophilic blocks arelinked to the lipophilic blocks via other chemical bonds.

[0341] As examples of nonionic fatty-chain polyether polyurethanes whichmay be used in the invention, mention may also be made of Rheolate 205containing a urea function, sold by the company Rheox, or the Rheolates208, 204 or 211, and also Acrysol RM 184, Aculyn or Acrysol 44 andAculyn or Acrysol 46 from the company Rohm & Haas [Aculyn 46 is apolycondensate of polyethylene glycol containing 150 or 180 mol ofethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexylisocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%)and water (81%); Aculyn 44 is a polycondensate of polyethylene glycolcontaining 150 or 180 mol of ethylene oxide, of decyl alcohol and ofmethylenebis(4-cyclohexyl-isocyanate) (SMDI), at 35% by weight in amixture of propylene glycol (39%) and water (26%)].

[0342] Mention may also be made of the product Elfacos T210 containing aC₁₂₋₁₄ alkyl chain, and the product Elfacos T212 containing a C₁₈ alkylchain, from Akzo.

[0343] The product DW 1206B from Rohm & Haas containing a C₂₀ alkylchain and urethane linkage, sold at a solids content of 20% in water,may also be used.

[0344] It is also possible to use solutions or dispersions of thesepolymers, especially in water or in aqueous-alcoholic medium. Examplesof such polymers which may be mentioned are Rheolate 255, Rheolate 278and Rheolate 244 sold by the company Rheox. The products DW 1206F and DW1206J sold by the company Rohm & Haas may also be used.

[0345] The polyether polyurethanes which may be used according to theinvention are in particular those described in the article by G. Formum,J. Bakke and Fk. Hansen—Colloid Polym. Sci 271, 380.389 (1993).

[0346] The amphiphilic polymers of cationic type comprising at least onefatty chain which are used in the present invention are preferablychosen from quaternized cellulose derivatives and polyacrylatescontaining acyclic amino side groups.

[0347] The quaternized cellulose derivatives are, in particular,

[0348] quaternized celluloses modified with groups comprising at leastone fatty chain, such as alkyl, aralalkyl or alkylaryl groups containingat least 8 carbon atoms, or mixtures thereof.

[0349] quaternized hydroxyethylcelluloses modified with groupscomprising at least one fatty chain, such as alkyl, aralalkyl oralkylaryl groups containing at least 8 carbon atoms, or mixturesthereof.

[0350] The alkyl radicals borne by the above quaternized celluloses orhydroxyethylcelluloses preferably contain from 8 to 30 carbon atoms. Thearyl radicals preferably denote phenyl, benzyl, naphthyl or anthrylgroups.

[0351] Examples of quaternized alkylhydroxyethylcelluloses containingC₈-C₃₀ fatty chains which may be mentioned include the productsQuatrisoft LM 200, Quatrisoft LM-X 529-18-A, Quatrisoft LM-X 529-18B(C₁₂ alkyl) and Quatrisoft LM-X 529 8 (C₁₈ alkyl) sold by the companyAmerchol, and the products Crodacel QM, Crodacel Q1 (C₁₂ alkyl) andCrodacel QS (C₁₈ alkyl) sold by the company Croda.

[0352] The polyacrylates containing quaternized or nonquaternized aminoside groups contain, for example, hydrophobic groups of the type such asSteareth 20 (polyoxyethylenated(20) stearyl alcohol).

[0353] Examples of polyacrylates containing amino side chains which maybe mentioned include the polymers 8781-121B and 9492-103 sold by thecompany National Starch.

[0354] In the oxidation dye composition according to the invention,among the fatty-chain amphiphilic polymers, it is preferred to use anamphiphilic polymer of nonionic or cationic type comprising at least onefatty chain.

[0355] According to the invention, the amphiphilic polymer(s) comprisingat least one fatty chain may represent about 0.01% to 10% by weightrelative to the total weight of the composition. Preferably, this amountranges from about 0.1% to 5% by weight.

[0356] Needless to say, a person skilled in the art will take care toselect this or these optional additional compound(s) such that theadvantageous properties intrinsically associated with the oxidation dyecomposition in accordance with the invention are not, or are notsubstantially, adversely affected by the envisaged addition(s).

[0357] The dye composition according to the invention may be in variousforms, such as in the form of liquids, creams or gels or any other formwhich is suitable for dyeing keratin fibers, and in particular humanhair.

[0358] A subject of the invention is also a process for dyeing keratinfibers, and in particular human keratin fibers such as the hair, usingthe dye composition as defined above.

[0359] According to this process, at least one dye composition asdefined above is applied to the fibers, the color being developed atacidic, neutral or alkaline pH with the aid of an oxidizing agent whichis added just at the time of use to the dye composition, or which ispresent in an oxidizing composition that is applied simultaneously orsequentially.

[0360] According to one preferred embodiment of the dyeing process ofthe invention, the dye composition described above is preferably mixed,at the time of use, with an oxidizing composition containing, in amedium which is suitable for dyeing, at least one oxidizing agentpresent in an amount which is sufficient to develop a coloration. Themixture obtained is then applied to the keratin fibers and left to standon them for 3 to 50 minutes approximately, preferably 5 to 30 minutesapproximately, after which the fibers are rinsed, washed with shampoo,rinsed again and dried.

[0361] The oxidizing agent may be chosen from the oxidizing agentsconventionally used for the oxidation dyeing of keratin fibers, andamong which mention may be made of hydrogen peroxide, urea peroxide,alkali metal bromates, persalts such as perborates and persulfates,peracids and enzymes, among which mention may be made of peroxidases,2-electron oxidoreductases such as uricases, and 4-electron oxygenases,for instance laccases. Hydrogen peroxide is particularly preferred.

[0362] The pH of the oxidizing composition containing the oxidizingagent as defined above is such that, after mixing with the dyecomposition, the pH of the resulting composition applied to the keratinfibers preferably ranges between 3 and 12 approximately, and even morepreferentially between 5 and 11. It is adjusted to the desired valuewith the aid of acidifying or basifying agents usually used for thedyeing of keratin fibers and as defined above.

[0363] The oxidizing composition as defined above may also containvarious adjuvants conventionally used in compositions for dyeing thehair and as defined above.

[0364] The composition which is finally applied to the keratin fibersmay be in various forms, such as in the form of liquids, creams or gels,or in any other form which is suitable for dyeing keratin fibers, andespecially human hair.

[0365] Another subject of the invention is a multi-compartment dyeing“kit” or any other multi-compartment packaging system, a firstcompartment of which contains the dye composition as defined above, anda second compartment of which contains the oxidizing composition asdefined above. These devices may be equipped with a means for deliveringthe desired mixture onto the hair, such as the devices described inpatent FR-2 586 913 in the name of the applicant.

[0366] Finally, a subject of the invention is also the colored productresulting from the oxidation of at least one compound of formula (I) asdefined above in the presence of at least one oxidizing agent as definedabove and optionally in the presence of at least one coupler and/or ofat least one optional oxidation base.

[0367] These colored products may especially be in the form of pigmentsand may be used as direct dyes for the direct dyeing of the hair, oralternatively may be incorporated into cosmetic products such as, forexample, make-up products.

[0368] The examples which follow are intended to illustrate theinvention.

EXAMPLES OF SYNTHESES EXAMPLE 1(4-Amino-3-methylphenyl)pyrrolidin-3-ylamine Dihydrochloride (3)

[0369]

[0370] Synthesis ofN-[1-(3-methyl-4-nitrophenyl)pyrrolidin-3-yl]acetamide (1):

[0371] After dissolving 15.5 g of 5-fluoro-2-nitrotoluene (0.1 mol) and12.8 g of 3-acetamido-pyrrolidine (0.1 mol) in 75 ml of NMP, 15.8 g ofpotassium carbonate (0.12 mol) are added under a nitrogen atmosphere andthe mixture is heated at 95° C. for 20 h. The reaction medium is allowedto cool and is then poured into 600 ml of saturated aqueous sodiumchloride solution. The yellow precipitate formed is filtered off, washedwith 15% NaCl solution until a pH equal to 7 is obtained for the washingwaters, and washed with petroleum ether and then dried in a vacuum ovenover P₂O₅. 25.7 g (98%) ofN-[1-(3-methyl-4-nitrophenyl)pyrrolidin-3-yl]acetamide are thus obtainedin the form of a yellow solid.

[0372] Synthesis of 1-(3-methyl-4-nitrophenyl)pyrrolidin-3-ylamine (2):

[0373] 24 g (0.0911 mol) ofN-[1-(3-methyl-4-nitrophenyl)pyrrolidin-3-yl]acetamide (1) areintroduced into a solution containing 75 ml of 37% hydrochloric acid and165 ml of water in a 500 ml three-necked flask. The reaction medium isheated at 90° C. for 2 hours 30 minutes. After cooling, the medium isneutralized carefully with 75 ml of aqueous 35% sodium hydroxide(pH=approximately 8). The resulting solid is then filtered off, afterwhich-it is washed with water until the washing waters are neutral. Theproduct is then dried under vacuum over P₂O₅. 16.8 g (83%) of1-(3-methyl-4-nitrophenyl)pyrrolidin-3-ylamine (2) are thus obtained inthe form of a yellow solid.

[0374] Synthesis of (4-amino-3-methylphenyl)pyrrolidin-3-ylamineDihydrochloride (3):

[0375] 16 g of 1-(3-methyl-4-nitrophenyl)pyrrolidin-3-ylamine (2) (72,3mmol) are partially dissolved in 320 ml of 960 ethanol in astainless-steel hydrogenation reactor. 4 g of 5% Pd/C (50% water) areadded and the reactor is closed and purged with nitrogen 3 times withstirring (1 600 rpm). The hydrogen is then introduced under a pressureof 5-6 bar at ambient temperature. The temperature rises to 35° C. andthen falls back to 27° C. over 1 hour. The reactor is then purged withnitrogen and the reaction medium is filtered under a nitrogenatmosphere, and the filtrate is immediately recovered in a solutioncontaining 27 ml of 37% hydrochloric acid and 200 ml of isopropanol. Thefiltrate is then concentrated until a precipitate is obtained. The solidis filtered off, washed with isopropanol and then with ethyl ether, anddried under vacuum in the presence of potassium hydroxide. 15 g (78%) of(4-amino-3-methylphenyl)pyrrolidin-3-ylamine dihydrochloride (3) arethus obtained in the form of a white solid. The 1H-NMR spectrum and themass spectrum are in accordance with the spectra for product (3).elemental analysis (MW = 264.198; C11H17N3 . 2HCl) % C % H % N % ClTheory 50.01 7.25 15.9  26.84 Found 48.29 7.84 14.23 24.37

Example 2 1-(4-Amino-3-methoxyphenyl)pyrrolidin-3-ol Dihydrochloride (3)

[0376]

[0377] Synthesis of 4-fluoro-2-methoxy-1-nitrobenzene (1):

[0378] 25 g (0.159 mol) of 5-fluoro-2-nitrophenol are added to 125 ml ofDMSO. 22.5 g (0.159 mol) of methyl iodide are then added, followed bydropwise addition, while keeping the temperature below 25° C., of 17.8 gof aqueous 50% potassium hydroxide solution. The mixture is stirred forone hour at ambient temperature and a further 22.5 g (0.159 mol) ofmethyl iodide are then added. After stirring for 24 hours, the reactionmedium is poured into 125 ml of water and then extracted with 60 ml ofdichloromethane. The organic phase is washed with 90 ml of aqueoussodium hydroxide solution (1N) and then with 60 ml of water. Afterdrying over MgSO₄, the organic phase is concentrated under reducedpressure. 20.59 g (76%) of 4-fluoro-2-methoxy-1-nitrobenzene (1) arethus recovered.

[0379] Synthesis of 1-(3-methoxy-4-nitrophenyl)pyrrolidin-3-ol (2):

[0380] 8 g (46 mmol) of 4-fluoro-2-methoxy-1-nitrobenzene 1,80 ml ofdioxane and 8.14 g (0.095 mol) of (R)-(+)-3-pyrrolidinol arerespectively placed in the reactor. The mixture is refluxed for onehour. The reaction medium is poured into a mixture of water (100 ml)-ice(200 g). A yellow product precipitates. This product is filtered off,washed with water (3×30 ml) and then dried under vacuum at 45° C. 8.38 g(75%) of 1-(3-methoxy-4-nitrophenyl)pyrrolidin-3-ol (2) are thusrecovered.

[0381] Synthesis of 1-(4-amino-3-methoxyphenyl)pyrrolidin-3-olDihydrochloride (3):

[0382] 12 g (0.05 mol) of 1-(3-methoxy-4-nitro-phenyl)pyrrolidin-3-ol(2), 36 ml of ethanol, 24 ml of cyclohexene and 5.4 g of 10% Pd/C (50%water) are respectively added to the reactor and the reaction medium isthen refluxed for 5 hours. The medium is then filtered through Celite,collecting the filtrate onto a 5N hydrochloric ethanol solution. TheCelite is washed with ethanol (3×20 ml). The organic phases are combinedand then concentrated until a yellow precipitate appears. After coolingto 0° C. and stirring for 1 hour, the product is filtered off, rinsedwith water and then dried under vacuum. 10.5 g (74.1%) of1-(4-amino-3-methoxyphenyl)pyrrolidin-3-ol dihydrochloride (3) are thusrecovered in the form of a slightly orange solid. The 1H-NMR spectrumand the mass spectrum are in accordance with the spectra for product(3). Elemental analysis (MW = 281.181; C11H16N2O2.2HCl) % C % H % N % O% Cl Theory 46.99 6.45 9.96 11.38 25.25 Found 46.88 6.83 9.58 11.2824.98

Example 3 (R)-1-(4-Aminophenyl)pyrrolidin-3-ol Dihydrochloride (2)

[0383]

[0384] Synthesis of (R)-1-(4-aminophenyl)pyrrolidin-3-ol Dihydrochloride(2):

[0385] 5 g (24 mmol) of (R)-1-(4-nitrophenyl)-pyrrolidin-3-ol and 1 g ofpalladium on charcoal are introduced, under a gentle stream of nitrogen,into a fully equipped 200 ml stainless-steel hydrogenator. 50 ml ofethanol are then added and the mixture is then stirred at 1 500 rpmwhile flushing three times with nitrogen and once with hydrogen.Hydrogen is then introduced under a pressure of 5.5 bar. Theexothermicity is allowed to develop to 55° C. After one hour 30 minutes,the temperature has fallen back to 31° C. The mixture is purged undernitrogen and then filtered through a closed filter under a nitrogenpressure of 2 bar. The filtrate is recovered in an ice-cold mixture of 7ml of concentrated hydrochloric acid and 21 ml of isopropanol. Thepartially crystalline mixture is transferred into a round-bottomed flaskwith 20 ml of additional isopropanol to be subsequently evaporatedtherefrom under reduced pressure. After concentrating, the productcrystallizes abundantly. Next, 40 ml of isopropanol are added and themixture is then left stirring overnight while flushing gently withnitrogen. The mixture is then filtered, spin-filtered, washed with 20 mlof isopropanol and dried under high vacuum (˜10 mmHg) at a temperatureof 40° C. 4.3 g (71%) of (R)-1-(4-aminophenyl)pyrrolidin-3-oldihydrochloride (2) are thus obtained. The 1H-NMR spectrum and massspectrum are in accordance with the spectra for product (3). % C % H % N% O % Cl Theory 47.82 6.82 11.15 6.37 28.23 Found 47.27 6.40 11.06 6.9927.95

Example 4 N-[1-(4-Aminophenyl)pyrrolidin-3-yl]-acetamide Dihydrochloride(2)

[0386]

[0387] Synthesis of N-[1-(4-nitrophenyl)pyrrolidin-3-yl]-acetamide (1):

[0388] After dissolving 56.4 g of 1-fluoro-4-nitrobenzene (0.4 mol) and51.2 g of 3-acetamidopyrrolidine (0.4 mol) in 400 ml of NMP, 66.4 g ofpotassium carbonate (0.48 mol) are added under a nitrogen atmosphere andthe mixture is heated at 100° C. for 18 hours. The reaction medium isallowed to cool and is then poured into 2 l of water. The yellowprecipitate formed is filtered off, washed with water and then dried ina vacuum oven over P₂O₅. 100 g (100%) ofN-[1-(4-nitrophenyl)pyrrolidin-3-yl]acetamide (1) are thus obtained inthe form of a yellow solid.

[0389] Synthesis of N-[1-(4-aminophenyl)pyrrolidin-3-yl]-acetamidemonohydrochloride (2):

[0390] 30 g of N-[1-(4-nitrophenyl)pyrrolidin-3-yl]-acetamide (1) (120mmol) are partially dissolved in 670 ml of absolute ethanol in astainless-steel hydrogenation reactor. 4.5 g of 5% Pd/C (50% water) areadded and the reactor is closed and purged with nitrogen 3 times withstirring (1 600 rpm). Hydrogen is then introduced to a pressure of 10bar at ambient temperature. The reaction medium is heated to 55° C. andis then cooled to 27° C. over 3 hours. The reactor is then purged withnitrogen and the reaction medium is filtered under a nitrogenatmosphere, and the filtrate is immediately recovered in 90 ml ofhydrochloric ethanol solution (5N). The filtrate is then concentrateduntil a precipitate is obtained. The solid is filtered off, washed withisopropanol and then with ethyl ether and dried under vacuum in thepresence of potassium hydroxide. 19.4 g (63%) ofN-[1-(4-amino-phenyl)pyrrolidin-3-yl]acetamide dihydrochloride (2) arethus obtained in the form of a white solid. The 1H-NMR spectrum and massspectrum are in accordance with the spectra for product (2). Elementalanalysis (MW = 292.208; C12H17N3O.2HCl) % C % H % N % O % Cl Theory49.33 6.55 14.38 5.48 24.27 Found 48.35 6.62 14.19 7.17 20.52

Example 5 [1-(4-Aminophenyl)pyrrolidin-3-yl]dimethylamineDihydrochloride (2)

[0391]

[0392] Synthesis of dimethyl-[1-(4-nitrophenyl)pyrrolidin-3-yl]amine(1):

[0393] 32.38 g of potassium carbonate (308 mmol) are added to a solutionof 250 ml of water containing 29.3 g of N,N-dimethylaminopyrrolidine(257 mmol) and 36.23 g of 4-fluoronitrobenzene (257 mmol), and themixture is then refluxed for 3 hours. The reaction medium dissolves anda product then precipitates. The product is filtered off and washed withwater. It is dried in a vacuum oven at 40° C. over P₂O₅. 55.9 g (92%) ofdimethyl-[1-(4-nitrophenyl)pyrrolidin-3-yl]amine (1) are thus obtainedin the form of a yellow solid.

[0394] Synthesis of [1-(4-aminophenyl)pyrrolidin-3-yl]dimethylamineDihydrochloride (2):

[0395] 50 g of dimethyl-[1-(4-nitrophenyl)-pyrrolidin-3-yl]amine (1)(212 mmol) are added to 500 ml of absolute ethanol in a stainless-steelhydrogenation reactor. 10 g of 5% Pd/C (50% water) are added and thereactor is closed and purged with nitrogen 3 times with stirring (1 600rpm). Hydrogen is then introduced at a pressure of 5-6 bar at ambienttemperature. The temperature rises to 35° C. and then falls back to 27°C. over 1 hour. The reactor is then purged with nitrogen and thereaction medium is filtered under a nitrogen atmosphere, and thefiltrate is recovered immediately in a solution containing 62 ml of 37%hydrochloric acid and 240 ml of isopropanol. The filtrate is thenconcentrated until a precipitate is obtained. The solid is filtered off,washed with isopropanol and then with ethyl ether and dried under vacuumat 50° C. in the presence of potassium hydroxide. 39.1 g (66%) of[1-(4-aminophenyl)pyrrolidin-3-yl]dimethylamine dihydrochloride (2) arethus obtained in the form of a white solid. The 1 H-NMR spectrum is inaccordance with the spectrum for the product. Elemental analysis (MW =278.225; C12H19N3 . 2HCl) % C % H % N % Cl Theory 51.8 7.61 15.1  25.49Found 51.2 7.73 14.83 25.46

Example 6 1-(4-Aminophenyl)pyrrolidin-3-ylamine Dihydrochloride (3)

[0396]

[0397] Synthesis of N-[1-(4-nitrophenyl)pyrrolidin-3-yl]acetamide (1):

[0398] After dissolving 56.4 g of 1-fluoro-4-nitrobenzene (0.4 mol) and51.2 g of 3-acetamido-pyrrolidine (0.4 mol) in 400 ml of NMP, 66.4 g ofpotassium carbonate (0.48 mol) are added under a nitrogen atmosphere andthe mixture is heated at 100° C. for 18 hours. The reaction medium isallowed to cool and is then poured into 2 l of water. The yellowprecipitate formed is filtered off, washed with water and then dried ina vacuum oven over P₂O₅. 100 g (100%) ofN-[1-(4-nitrophenyl)pyrrolidin-3-yl]acetamide (1) are thus obtained inthe form of a yellow solid.

[0399] Synthesis of 1-(4-nitrophenyl)pyrrolidin-3-ylamine (2):

[0400] 100 g (0.4 mol) of N-[1-(4-nitrophenyl)-pyrrolidin-3-yl]acetamide(1) are introduced as a suspension into a solution containing 300 ml of37% hydrochloric acid and 660 ml of water in a 2 l three-necked flask.The reaction medium is heated at 90° C. for 7 hours 45 minutes. Aftercooling, the medium is neutralized carefully with 300 ml of aqueous 35%sodium hydroxide (pH=approximately 8). The resulting solid is thenfiltered off, after which it is washed with water (until the washingwaters are neutral). The product is then dried under vacuum over P₂O₅.74 g (89%) of 1-(4-nitrophenyl)pyrrolidin-3-ylamine (2) are thusobtained in the form of a yellow solid.

[0401] Synthesis of 1-(4-aminophenyl)pyrrolidin-3-ylamineDihydrochloride (3):

[0402] 72 g of 1-(4-nitrophenyl)pyrrolidin-3-ylamine (2) (347 mmol) areadded to 600 ml of methanol in a stainless-steel hydrogenation reactor.15 g of 5% Pd/C (50% water) are added and the reactor is closed andpurged with nitrogen 3 times with stirring (1 600 rpm). Hydrogen is thenintroduced at a pressure of 5 bar at ambient temperature. Thetemperature rises to 52° C. and then falls back to 38° C. over 2 hours50 minutes. The reactor is then purged with nitrogen and the reactionmedium is filtered under a nitrogen atmosphere, and the filtrate isimmediately recovered in a solution containing 130 ml of 37%hydrochloric acid, 200 ml of isopropanol and 200 ml of absolute ethanol.The filtrate is then concentrated until a precipitate is obtained. Thesolid is filtered off, washed with isopropanol and then with ethyl etherand dried under vacuum at 50° C. in the presence of potassium hydroxide.71 g (82%) of 1-(4-aminophenyl)pyrrolidin-3-ylamine dihydrochloride (3)are thus obtained in the form of a white solid. The 1 H-NMR spectrum andmass spectrum are in accordance with product (3). Elemental analysis (MW= 250.171; C10H15N3 . 2HCl) % C % H % N % Cl Theory 48.01 6.85 16.828.34 Found 46.33 6.78 16.5 28.97

Example 7 Synthesis of 1-(4-aminophenyl)pyrrolidin-3-ol Hydrochloride

[0403]

[0404] Step 1: Preparation of 1-(4-nitrophenyl)pyrrolidin-3-ol

[0405] 2 g of 1-fluoro-4-nitrobenzene (0.0155 mol), 1.3 g of sodiumhydrogen carbonate (0.0155 mol) and 15 ml of a dioxane/water mixture(8/2) were introduced into a three-necked flask. 1.35 g of racemic3-pyrrolidinol (0.0155 mol) were rapidly added to this mixture. Theheterogeneous mixture was refluxed (87° C.) for 10 hours. The reactionmixture was then poured into ice-cold water; a yellow precipitate wasobtained, which was filtered off and rinsed with water. After dryingunder vacuum in the presence of P₂O₅, 2.95 g of a yellow solid wereobtained (97% yield).

[0406]¹H NMR analysis (DMSO-d₆, 200 MHz, ppm), in accordance with theexpected product, was as follows:

[0407] 8.04 (d, J=9 Hz, 2H); 6.58 (d, J=9 Hz, 2H); 5.06 (d, J=3.6 Hz,1H); 4.41 (m, 1H); 3.45 (m, 3H); 3.20 (m, 1H); 2.04 (m, 2H).

[0408] The elemental analysis was as follows: % C H N O Calculated 57.895.81 13.45 23.05 Found 57.17 5.72 13.23 23.28

[0409] Step 2: Preparation of 1-(4-aminophenyl)pyrrolidin-3-olHydrochloride

[0410] The 1-(4-nitrophenyl)pyrrolidin-3-ol obtained above in thepreceding step (2 g, 9.605 mmol) was suspended in 40 ml of absoluteethanol and 8 ml of cyclohexene, and in the presence of 1 g of wetpalladium-on-charcoal. Argon was then bubbled into the reaction mediumfor a few minutes, followed by refluxing for 4 hours. The reactionmixture was filtered into a vacuum flask containing 100 ml ofdiisopropyl ether, 50 ml of isopropanol and 4 equivalents ofhydrochloric ethanol (6.2 ml) cooled to −5° C. The precipitate obtainedwas filtered quickly and dried in a vacuum oven at 30° C. 1.22 g of aslightly pink solid were obtained in a yield of 59%, the melting pointof which is greater than 200° C.

[0411] The ¹H NMR analysis (MeOH-d₄, 200 MHz, ppm) in accordance withthe expected product, was as follows:

[0412] 7.26 (d, J=9 Hz, 2H); 7.08 (d, J=9 Hz, 2H), 4.48 (m, 1H); 3.54(m, 3H); 3.30 (m, 1H); 2.09 (m, 2H).

[0413] The elemental analysis was as follows: % C H N O Cl Calculated48.18 6.70 11.24 9.64 24.23 Found 48.54 6.62 11.16 9 24.67

[0414] The product obtained contains 1.7 molecules of HCl and 0.5molecule of water.

Example 8 Synthesis of 1-(4-amino-2-methylphenyl)-pyrrolidin-3-olHydrochloride

[0415]

[0416] Step 1: Preparation of 1-(4-nitro-2-methylphenyl)-pyrrolidin-3-ol

[0417] 2.4 g of 1-fluoro-2-methyl-4-nitrobenzene (0.0155 mol), 1.3 g ofsodium hydrogen carbonate (0.0155 mol) and 15 ml of a dioxane/watermixture (8/2) were introduced into a three-necked flask. 1.35 g ofracemic 3-pyrrolidinol (0.0155 mol) were rapidly added to this mixture.The heterogeneous mixture was refluxed (87° C.) for 24 hours. Thereaction mixture was then poured into ice-cold water; an orangeprecipitate was obtained, which was filtered off and rinsed with water.After drying under vacuum in the presence of P₂O₅, 3.19 g of an orangesolid were obtained (93% yield).

[0418] The ¹H NMR analysis (DMSO-d₆, 200 MHz, ppm), in accordance withthe expected product, was as follows:

[0419] 7.80 (m, 2H); 6.58 (m, 1H); 4.91 (d, J=3.3 Hz, 1H); 4.25 (m, 1H),3.60 (m, 2H); 3.41 (m, 1H); 3.18 ppm (m, 1H); 2.34 (s, 3H); 1.82 (m, 2H)

[0420] The elemental analysis was as follows: % C H N O Calculated 59.456.35 12.60 21.60 Found 58.91 6.40 12.20 21.42

[0421] Step 2: Preparation of 1-(4-amino-2-methylphenyl)-pyrrolidin-3-olHydrochloride

[0422] The 1-(4-nitro-2-methylphenyl)pyrrolidin-3-ol obtained above inthe preceding step (2 g, 9.00 mmol) was suspended in 40 ml of absoluteethanol and 8 ml of cyclohexene, and in the presence of 1 g of wetpalladium-on-charcoal. Argon was then bubbled through the reactionmedium for a few minutes, followed by refluxing for 4 hours. Thereaction mixture was filtered into a vacuum flask containing 100 ml ofdiisopropyl ether, 50 ml of isopropanol and 4 equivalents ofhydrochloric ethanol (6.2 ml) cooled to −5° C. The precipitate obtainedwas filtered quickly and dried in a vacuum oven at 30° C. 1.20 g of aslightly pink solid were obtained in a yield of 58%.

[0423] The ¹H NMR analysis (MeOH-d₄, 200 MHz, ppm), in accordance withthe expected product, was as follows:

[0424] 7.79 (d, J=9 Hz, 1H); 7.28 (m, 2H); 4.58 (m, 1H): 3.94 (m, 2H);3.53 (m, 1H); 3.13 (m, 1H); 2.48 (s, 3H); 2.20 (m, 2H).

[0425] The elemental analysis was as follows: % C H N O Cl Calculated46.80 7.09 9.93 11.34 24.82 Found 46.58 7.31 9.39 11.26 23.34

[0426] The product obtained contains 2 molecules of HCl and 1 moleculeof water.

Example 9 Synthesis of 1-(4-amino-3-methylphenyl)-pyrrolidin-3-olHydrochloride

[0427]

[0428] Step 1: Preparation of 1-(4-nitro-3-methylphenyl)-pyrrolidin-3-ol

[0429] 1.90 ml of 1-fluoro-3-methyl-4-nitrobenzene (0.0155 mol), 1.3 gof sodium hydrogen carbonate (0.0155 mol) and 15 ml of a dioxane/watermixture (8/2) were introduced into a three-necked flask. 1.35 g ofracemic 3-pyrrolidinol (0.0155 mol) were rapidly added to this mixture.The heterogeneous mixture was refluxed (87° C.) for 24 hours. Thereaction mixture was then poured into ice-cold water; a yellowprecipitate was obtained, which was filtered off and rinsed with water.After drying under vacuum in the presence of P₂O₅, 2.7 g of a yellowsolid were obtained (78% yield).

[0430] The ¹H NMR analysis (DMSO-d₆, 200 MHz, ppm), in accordance withthe expected product, was as follows:

[0431] 8.03 (d, J=9 Hz, 1H); 6.52 (m, 2H); 5.08 (d, J=3.2, 1H); 4.44 (m,1H); 3.50 (m, 3H); 3.25 (m, 1H); 2.58 (s, 3H); 2.05 (m, 2H).

[0432] The elemental analysis was as follows: % C H N O Calculated 59.456.35 12.60 21.60 Found 58.82 6.48 12.16 21.50

[0433] Step 2: Preparation of 1-(4-amino-3-methylphenyl)-pyrrolidin-3-olHydrochloride

[0434] The 1-(4-nitro-3-methylphenyl)pyrrolidin-3-ol obtained above inthe preceding step (2 g, 9.00 mmol) was suspended in 40 ml of absoluteethanol and 8 ml of cyclohexene, and in the presence of 1 g of wetpalladium-on-charcoal. Argon was then bubbled through the reactionmedium for a few minutes, followed by refluxing for 4 hours. Thereaction mixture was filtered into a vacuum flask containing 100 ml ofdiisopropyl ether, 50 ml of isopropanol and 4 equivalents ofhydrochloric ethanol (6.2 ml) cooled to −5° C. The precipitate obtainedwas filtered off rapidly and dried in a vacuum oven at 30° C. 1.93 g ofa slightly pink solid were obtained in a yield of 94%.

[0435] The ¹H NMR analysis (MeOH-d₄, 200 MHz, ppm), in accordance withthe expected product, was as follows:

[0436] 7.44 (m, 1H); 7.33 (m, 2H); 4.66 (m, 1H): 3.79 (m, 3H); 3.52 (m,1H); 2.45 (s, 3H); 2.37 (m, 2H).

[0437] The elemental analysis was as follows: % C H N O Cl Calculated46.80 7.09 9.93 11.36 24.82 Found 47.49 6.95 9.66 11.32 24.56

[0438] The product obtained contains 2 molecules of HCl and 1 moleculeof water.

Dyeing Examples

[0439] The dye compositions below in accordance with the invention, wereprepared: Examples 1 2 3 (4-Amino-3-methylphenyl)- 3 × 10⁻³ 3 × 10⁻³ 3 ×10⁻³ pyrrolidin-3-ylamine, dihydrochloride Resorcinol 3 × 10⁻³1-β-Hydroxyethyloxy-2,4- 3 × 10⁻³ diaminobenzene 1-Methyl-4-aminophenol3 × 10⁻³ Common dye support (*) (*) (*) Demineralized water qs 100 g 100g 100 g Examples 4 5 6 7 1-(4-Amino-3- 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ 3 ×10⁻³ methoxyphenyl)- pyrrolidin-3-ol, dihydrochloride Resorcinol 3 ×10⁻³ — — — 1-β-Hydroxyethyloxy-2, — 3 × 10⁻³ — — 4-diaminobenzene1-Methyl-4-aminophenol — — 3 × 10⁻³ — Common dye support (*) (*) (*) (*)Demineralized water qs 100 g 100 g 100 g 100 g Examples 8 9 10(R)-1-(4-Aminophenyl)pyrrolidin- 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ 3-ol,dihydrochloride Resorcinol 3 × 10⁻³ 1-β-Hydroxyethyloxy-2,4- 3 × 10⁻³diaminobenzene 1-Methyl-4-aminophenol 3 × 10⁻³ Common dye support (*)(*) (*) Demineralized water qs 100 g 100 g 100 g Examples 11 12N-[1-(4-Aminophenyl)pyrrolidin-3- 3 × 10⁻³ 3 × 10⁻³ yl] acetamidedihydrochloride Resorcinol 3 × 10⁻³ 1-β-Hydroxyethyloxy-2,4-diamino- 3 ×10⁻³ benzene Common dye support (*) (*) Demineralized water qs 100 g 100g Examples 13 14 15 16 [1-(4-Aminophenyl) 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ 3 ×10⁻³ pyrrolidin- 3-yl] dimethylamine dihydrochloride Resorcinol 3 × 10⁻³— — — 1-β-Hydroxyethyloxy-2, — 3 × 10⁻³ — — 4-diaminobenzene1-Methyl-4-aminophenol — — 3 × 10⁻³ — Common dye support (*) (*) (*) (*)Demineralized water qs 100 g 100 g 100 g 100 g Examples 17 18 19 201-(4-Aminophenyl) 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ pyrrolidin-3-ylamine dihydrochloride Resorcinol 3 × 10⁻³ — — —1-β-Hydroxyethyloxy-2, — 3 × 10⁻³ — — 4-diaminobenzene1-Methyl-4-aminophenol — — 3 × 10⁻³ — Common dye support (*) (*) (*) (*)Demineralized water qs 100 g 100 g 100 g 100 g Examples 21 22 23 241-(4-Aminophenyl) 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ 3 × 10⁻³ pyrrolidin-3-ol,dihydochloride Resorcinol 3 × 10⁻³ — — — 1-β-Hydroxyethyloxy-2, — 3 ×10⁻³ — — 4-diaminobenzene 1-Methyl-4-aminophenol — — 3 × 10⁻³ — Commondye support (*) (*) (*) (*) Demineralized water qs 100 g 100 g 100 g 100g (*) Common dye support: Oleyl alcohol polyglycerolated with 4.0 g 2mol of glycerol Oleyl alcohol polyglycerolated with 5.69 g A.M. 4 mol ofglycerol, containing 78% active material (A.M.) Oleic acid 3.0 gOleylamine containing 2 mol of ethylene 7.0 g oxide, sold under thetrade name Ethomeen O12 ® by the company Akzo Diethylaminopropyl 3.0 gA.M. laurylaminosuccinamate, sodium salt containing 55% A.M. Oleylalcohol 5.0 g Oleic acid diethanolamide 12.0 g Propylene glycol 3.5 gEthyl alcohol 7.0 g Dipropylene glycol 0.5 g Propylene glycol monomethylether 9.0 g Sodium metabisulphite as an aqueous 0.455 g A.M. solutioncontaining 35% A.M. Ammonium acetate 0.8 g Antioxidant, sequesteringagent qs Fragrance, preserving agent qs Aqueous ammonia containing 20%NH₃ 10.2 g

[0440] At the time of use, each dye composition was mixed with an equalamount of an oxidizing composition consisting of a 20-volumes aqueoushydrogen peroxide solution (6% by weight) with a pH of about 3.

[0441] Each mixture obtained has a pH of about 9.5. Each mixture isapplied to locks of natural gray hair containing 90% white hairs. Afterleaving the mixture to stand on the locks for 30 minutes, the locks ofhair are rinsed, washed with a standard shampoo, rinsed and then dried.

[0442] The colour of the locks was evaluated in the L*a*b* system usinga Minolta CM 2002® spectro-photometer (Illuminant D65).

[0443] In the L*a*b* system, the three parameters denote, respectively,the intensity (L*), the red-green chromatic component (a*) and theyellow-blue chromatic component (b*). According to this system, thehigher the value of L, the paler or less intense the color. Conversely,the smaller the value of L, the darker or more intense the color.Natural white hairs Examples L* a* b* Ex. 1 35.2 3.8 6.1 Ex. 2 23.8 −1.9−8.3 Ex. 3 25.4 4.8 −10.45 Ex. 4 33.5 0.4 −4.9 Ex. 5 26.2 −3.3 −11.5 Ex.6 29.5 −0.5 −13.3 Ex. 7 48.2 2.6 6.8 Ex. 8 28.2 4.0 0.3 Ex. 9 22.2 2.1−13.3 Ex. 10 20.1 3.5 −8.0 Ex. 11 31.3 3.9 1.2 Ex. 12 23.2 0.06 −13.05Ex. 13 37.35 5.4 5.6 Ex. 14 26.0 0.01 −11.8 Ex. 15 34.6 8.0 −6.3 Ex. 1649.2 2,5 8.75 Ex. 17 29.9 5.45 3.4 Ex. 18 22.1 2.22 −12.8 Ex. 19 24.18.1 −9.7 Ex. 20 40.9 3.3 6.7 Ex. 21 29.9 4.44 0.58 Ex. 22 23.6 0.7 −13.8Ex. 23 22.9 5.8 −14.2 Ex. 24 47.6 1.0 8.45

[0444] The dye compositions below, in accordance with the invention,were prepared: Examples 25 26 27 28 29 30 N-(4-Aminophenyl)- 3 10⁻³ 310⁻³ — — — — 3-hydroxylpyrrolidine, mol mol dihydrochloride (compound offormula (I)) N-(4-Amino-2-methylphenyl)- — — 3 10⁻³ 3 10⁻³ — —3-hydroxylpyrrolidine, mol mol dihydrochloride (compound of formula (I))N-(4-Amino-3-methylphenyl)- — — — — 3 10⁻³ 3 10⁻³ 3-hydroxylpyrrolidine,mol mol dihydrochloride (compound of formula (I))2,4-Diamino-1-(β-hydroxy- 3 10⁻³ — 3 10⁻³ — 3 10⁻³ — ethyloxy)benzene,mol mol mol dihydrochloride (coupler) 1,3-Dihydroxybenzene (coupler) — 310⁻³ — 3 10⁻³ — 3 10⁻³ mol mol mol Common dye support (*) (*) (*) (*)(*) (*) Demineralized water qs 100 g 100 g 100 g 100 g 100 g 100 g

[0445] At the time of use, each dye composition is mixed with an equalamount of an oxidizing composition consisting of a 20 volumes aqueoushydrogen peroxide solution (6% by weight) with a pH of about 3.

[0446] Each mixture obtained has a pH of about 9.5, and is applied tolocks of natural gray hair containing 90% white hairs. After 30 minutes,the locks of hair are then rinsed, washed with a standard shampoo andthen dried.

[0447] The locks of hair were dyed in the shades given in the tablebelow: EXAMPLE SHADE ON NATURAL HAIR 25 Blue 26 Ash violet iridescentblonde 27 Ash light blue 28 Very slightly golden ash beige 29 Slightlymatt blue 30 Slightly golden ash grey

1. A composition for the oxidation dyeing of keratin fibers, and inparticular of human keratin fibers such as the hair, characterized inthat it comprises, in a medium which is suitable for dyeing, at leastone oxidation base chosen from para-phenylenediamine derivativescontaining a pyrrolidinyl group of formula (I) below, and the additionsalts thereof with an acid:

in which: R₁ represents a hydrogen atom; a halogen atom chosen from achlorine atom and a bromine atom; a linear or branched C₁-C₇ alkylradical (the branch(es) possibly forming one or more 3- to 6-memberedcarbon-based rings), which may contain one or more double bonds and/orone or more triple bonds (said double bonds optionally being able tolead to aromatic groups), one or more carbon atoms of which may bereplaced with an oxygen, nitrogen or sulfur atom or with an SO₂ group,and the carbon atoms of which may be, independently of each other,substituted with one or more halogen atoms; said radical R₁ containingno peroxide bond or diazo, nitro or nitroso radicals; R₂ represents ahydroxyl radical; an amino radical; a group —OR₃ in which R₃ representsa linear or branched C₁-C₄ alkyl radical substituted with one or moreradicals chosen from the group consisting of a halogen atom, C₁-C₂alkoxy, amino or C₁-C₂ aminoalkyl or a C₃-C₄ alkyl radical substitutedwith one or more hydroxyl radicals; a methylcarbonyl radical; a group—NR₄R₅ in which R₄ and R₅ represent, independently of each other, ahydrogen atom, a linear or branched C₁-C₄ alkyl radical substituted withone or more radicals chosen from the group consisting of a halogen atomand a hydroxyl, C₁-C₂ alkoxy, amino or C₁-C₂ aminoalkyl radical.
 2. Thecomposition as claimed in claim 1, characterized in that, in formula(I), R₁ represents a hydrogen atom or a methyl, ethyl, isopropyl, vinyl,allyl, methoxymethyl, hydroxymethyl, 1-carboxymethyl, 1-aminomethyl,2-carboxyethyl, 2-hydroxyethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl,1-hydroxy-2-aminoethyl, methoxy, ethoxy, allyloxy or 3-hydroxyethyloxyradical.
 3. The composition as claimed in claim 2, characterized inthat, in formula (I), R₁ represents a hydrogen atom or a methyl,hydroxymethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, methoxy or2-hydroxyethoxy radical.
 4. The composition as claimed in any one ofclaims 1 to 3, characterized in that, in formula (I), R₂ represents ahydroxyl radical; an amino radical; a group —OR₃ in which R₃ representsa linear or branched C₁-C₄ alkyl radical substituted with one or moreradicals chosen from the group consisting of a halogen atom, C₁-C₂alkoxy, amino and C₁-C₂ aminoalkyl; a methylcarbonyl radical; a group—NR₄R₅ in which R₄ and R₅ represent, independently of each other, ahydrogen atom, a linear or branched C₁-C₄ alkyl radical substituted withone or more radicals chosen from the group consisting of a halogen atomand a hydroxyl, C₁-C₂ alkoxy, amino or C₁-C₂ aminoalkyl radical.
 5. Thecomposition as claimed in claim 4, in which R₂ represents a hydroxyl,acetoxy, amino, methylamino, dimethylamino or 2-hydroxyethylaminoradical.
 6. The composition as claimed in any one of the precedingclaims, characterized in that the para-phenylenediamine derivativescontaining a pyrrolidinyl group of formula (I) are chosen fromN-(4-aminophenyl)-3-hydroxypyrrolidine,N-(4-amino-2-methylphenyl)-3-hydroxypyrrolidine,N-(4-amino-2-ethylphenyl)-3-hydroxypyrrolidine,N-(4-amino-2-methoxyphenyl)-3-hydroxypyrrolidine,N-(4-amino-2-(2-hydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-2-(1-hydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-2-(1,2-dihydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-methylphenyl)-3-hydroxypyrrolidine,N-(4-amino-3-ethylphenyl)-3-hydroxypyrrolidine,N-(4-amino-3-methoxyphenyl)-3-hydroxypyrrolidine,N-(4-amino-3-(2-hydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-(1-hydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-(1,2-dihydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-aminophenyl)-3-aminopyrrolidine,N-(4-amino-2-methylphenyl)-3-aminopyrrolidine,N-(4-amino-2-ethylphenyl)-3-aminopyrrolidine,N-(4-amino-2-methoxyphenyl)-3-aminopyrrolidine,N-(4-amino-2-(2-hydroxyethyl)-phenyl)-3-aminopyrrolidine,N-(4-amino-2-(1-hydroxyethyl)phenyl)-3-aminopyrrolidine,N-(4-amino-2-(1,2-dihydroxyethyl)phenyl)-3-hydroxypyrrolidine,N-(4-amino-3-methylphenyl)-3-aminopyrrolidine,N-(4-amino-3-ethylphenyl)-3-aminopyrrolidine,N-(4-amino-3-methoxyphenyl)-3-aminopyrrolidine,N-(4-amino-3-(2-hydroxyethyl)phenyl)-3-aminopyrrolidine,N-(4-amino-3-(1-hydroxyethyl)phenyl)-3-aminopyrrolidine andN-(4-amino-3-(1,2-dihydroxyethyl)phenyl)-3-aminopyrrolidine, and theaddition salts thereof with an acid.
 7. The composition as claimed inany one of the preceding claims, characterized in that thepara-phenylenediamine derivative(s) containing a pyrrolidinyl group offormula (I) and/or the addition salt(s) thereof with an acidrepresent(s) from 0.0005% to 12% by weight relative to the total weightof the dye composition, and preferably from 0.005% to 6%.
 8. Thecomposition as claimed in any one of the preceding claims, characterizedin that it contains one or more couplers chosen frommeta-phenylenediamines, meta-aminophenols, meta-diphenols andheterocyclic couplers.
 9. The composition as claimed in any one of thepreceding claims, in which the additional coupler is chosen fromheterocyclic couplers, substituted meta-diphenols, substitutedmeta-phenylenediamines, naphthols, acylated naphthols and themeta-aminophenols of formula III below

in which: R₅ represents a hydrogen atom or a C₁-C₄ alkyl, C₁-C₄monohydroxyalkyl or C₂-C₄ polyhydroxyalkyl radical, R₆ represents ahydrogen atom, a C₁-C₄ alkyl or C₁-C₄ alkoxy radical or a halogen atomchosen from chlorine, bromine and fluorine, R₇ represents a hydrogenatom or a C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ monohydroxyalkyl, C₂-C₄polyhydroxyalkyl, C₁-C₄ monohydroxyalkoxy or C₂-C₄ polyhydroxyalkoxyradical.
 10. The composition as claimed in claim 8 or 9, characterizedin that the couplers are chosen from 2-methyl-5-aminophenol,5-N—(β-hydroxyethyl)amino-2-methylphenol, 3-aminophenol,1,3-dihydroxybenzene, 1,3-dihydroxy-2-methylbenzene,4-chloro-1,3-dihydroxybenzene, 2,4-diamino-1-(β-hydroxyethyloxy)benzene,2-amino-4-(β-hydroxyethylamino)-1-methoxybenzene, 1,3-diaminobenzene,1,3-bis(2,4-diaminophenoxy)propane, sesamol, α-naphthol,2-methyl-1-naphthol, 6-hydroxyindole, 4-hydroxyindole,4-hydroxy-N-methylindole, 6-hydroxyindoline,2,6-dihydroxy-4-methylpyridine, 1H-3-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one, 2-amino-3-hydroxypyridine,3,6-dimethylpyrazolo[3,2-c]-1,2,4-triazole and2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole, and the addition saltsthereof with an acid.
 11. The composition as claimed in claim 8 to 10,characterized in that the coupler(s) represent(s) from 0.0001% to 10% byweight relative to the total weight of the dye composition.
 12. Thecomposition as claimed in claim 11, characterized in that the coupler(s)represent(s) from 0.005% to 5% by weight relative to the total weight ofthe dye composition.
 13. The composition as claimed in any one of thepreceding claims, characterized in that it contains at least oneadditional oxidation base chosen from para-phenylenediamines other thanthe compounds of formula (I) as defined in any one of claims 1 to 5,bis(phenyl)alkylenediamines, para-aminophenols, ortho-aminophenols andheterocyclic bases, and the addition salts thereof with an acid.
 14. Thecomposition as claimed in claim 13, in which the additional base ischosen from heterocyclic oxidation bases, double bases, substitutedpara-aminophenols, ortho-aminophenols, the para-phenylenediaminederivatives of formula (II) below, and the addition salts thereof withan acid:

in which: R₅ represents a hydrogen atom, a C₁-C₄ alkyl radical, a C₁-C₄monohydroxyalkyl radical, a C₂-C₄ poly-hydroxyalkyl radical, a(C₁-C₄)alkoxy(C₁-C₄)alkyl radical, a C₁-C₄ alkyl radical substitutedwith one or more nitrogenous groups, a phenyl radical or a4′-aminophenyl radical; R₆ represents a hydrogen atom, a C₁-C₄ alkylradical, a C₁-C₄ monohydroxyalkyl radical, a C₂-C₄ poly-hydroxyalkylradical, a (C₁-C₄)alkoxy(C₁-C₄)alkyl radical or a C₁-C₄ alkyl radicalsubstituted with one or more nitrogenous groups; R₇ represents ahydrogen atom, a halogen atom such as a chlorine, bromine, iodine orfluorine atom, a C₁-C₄ alkyl radical, a C₁-C₄ monohydroxyalkyl radical,a C₁-C₄ hydroxyalkoxy radical, an acetylamino(C₁-C₄)alkoxy radical, aC₁-C₄ mesylaminoalkoxy radical or a carbamoylamino (C₁-C₄) alkoxyradical, R₈ represents a hydrogen or halogen atom or a C₁-C₄ alkylradical.
 15. The composition as claimed in claim 13 or 14, characterizedin that the additional oxidation base(s) represent(s) from 0.0005% to12% by weight relative to the total weight of the dye composition. 16.The composition as claimed in any one of the preceding claims,characterized in that the addition salts with an acid are chosen fromthe hydrochlorides, hydrobromides, sulfates, citrates, succinates,tartrates, lactates, phosphates and acetates.
 17. The composition asclaimed in any one of the preceding claims comprising at least onepolymer chosen from: (i) amphoteric polymers, (ii) cationic polymerscontaining repeating units of structures (II) or (III) below, and (iii)polymers other than the above, which are amphiphilic and comprise atleast one fatty chain, Structure (II):

in which: R₅, R₆, R₇ and R₈, which may be identical or different,represent aliphatic, alicyclic or arylaliphatic radicals containing from1 to 20 carbon atoms or lower hydroxyalkylaliphatic radicals, oralternatively R₅, R₆, R₇ and R₈, together or separately, constitute,with the nitrogen atoms to which they are attached, heterocyclesoptionally containing a second hetero atom other than nitrogen, oralternatively R₅, R₆, R₇ and R₈ represent a linear or branched C₁-C₆alkyl radical substituted with a nitrile, ester, acyl, amide or—CO—O—R₁₃—D or —CO—NH—R₁₃—D group in which R₁₃ is an alkylene and D is aquaternary ammonium group; A₁ and B₁ represent polymethylene groupscontaining from 2 to 20 carbon atoms which may be linear or branched,saturated or unsaturated and which may contain, linked to orintercalated in the main chain, one or more aromatic rings, or one ormore oxygen or sulfur atoms or sulfoxide, sulfone, disulfide, amino,alkylamino, hydroxyl, quaternary ammonium, ureido, amide or estergroups. A₁, R₅ and R₇ may form with the two nitrogen atoms to which theyare attached a piperazine ring; in addition, if A₁ denotes a linear orbranched, saturated or unsaturated alkylene or hydroxyalkylene radical,B₁ can also denote a group —(CH₂)_(n)—CO—T—OC—(CH₂)_(n)— in which n isbetween 1 and 100 and preferably between 1 and 50, and T denotes: a) aglycol residue of formula: —O—Z—O—, in which Z denotes a linear orbranched hydrocarbon-based radical or a group corresponding to one ofthe following formulae:—(CH₂—CH₂—O)x-CH₂—CH₂——[CH₂—CH(CH₃)—O]y-CH₂—CH(CH₃)— in which x and ydenote an integer from 1 to 4, representing a defined and unique degreeof polymerization, or any number from 1 to 4 representing an averagedegree of polymerization; b) a bis-secondary diamine residue such as apiperazine derivative; c) a bis-primary diamine residue of formula:—NH—Y—NH—, in which Y denotes a linear or branched hydrocarbon-basedradical, or alternatively the divalent radical —CH₂—CH₂—S—S—CH₂—CH₂—; d)a ureylene group of formula: —NH—CO—NH—; X₁ ⁻ is an anion derived from amineral or organic acid and preferably chlorine or bromine; Structure(III)

in which: R₉, R₁₀, R₁₁ and R₁₂, which may be identical or different,represent a hydrogen atom or a methyl, ethyl, propyl, β-hydroxyethyl,β-hydroxypropyl or —CH₂CH₂(OCH₂CH₂)pOH radical, in which p is equal to 0or to an integer between 1 and 6, with the proviso that R₉, R₁₀, R₁₁ andR₁₂ do not simultaneously represent a hydrogen atom, r and s, which maybe identical or different, are integers between 1 and 6, D is zero ordenotes a group —(CH₂)_(q)—CO— in which q is zero or equal to an integerbetween 1 and 34, A denotes a dihalide radical or, preferably,represents —CH₂—CH₂—O—CH₂—CH₂—, X₂ ⁻ denotes an anion derived from amineral or organic acid, preferably a halogen atom.
 18. A process forthe oxidation dyeing of keratin fibers, characterized in that at leastone dye composition as defined in any one of claims 1 to 17 is appliedto said fibers and in that the color is revealed at acidic, neutral oralkaline pH with the aid of an oxidizing agent which is added just atthe time of use to the dye composition, or which is present in anoxidizing composition that is applied simultaneously or sequentially.19. The process as claimed in claim 18, characterized in that theoxidizing agent present in the oxidizing composition is chosen fromhydrogen peroxide, urea peroxide, alkali metal bromates, persalts,peracids and enzymes.
 20. A multi-compartment device ormulti-compartment dyeing “kit”, a first compartment of which contains adye composition as defined in any one of claims 1 to 17, and a secondcompartment of which contains an oxidizing composition.
 21. A coloredproduct resulting from the oxidation of at least one compound of formula(I) as defined in any one of claims 1 to 5, in the presence of at leastone oxidizing agent, and optionally in the presence of at least onecoupler and/or of at least one additional oxidation base.